Graphyne is a two-dimensional carbon allotropy that consists of different hybrid forms of carbon atoms in topological order. In different kinds of graphyne, carbon atoms undergo a rich bonding process through sp and sp2 hybridization, i.e., aromatic bonds, single bonds, and triple bonds, forming electron covalent frameworks and pores. Different bond lengths provide a higher structural flexibility and make coordination environmental regulation easier. For instance, the coexistence of sp and sp2 hybrid carbon atoms in graphdiyne (i.e., a typical and only artificially synthesized graphyne) makes the surface local electrons distributed unevenly, which makes it possible to design chemical reactions, site selective doping, and controllable atomic loading. The effective synthesis of graphdiyne (GDY) has thus brought a vitality to the research and development of carbon materials, providing a platform for carbon materials in various fields such as energy conversion and storage, optics, electronics, and magnetism, and having opportunities for the development of transformative materials. This unique alkyne bond rich structure provides almost infinite possibilities for the precise GDY tailoring towards different specific application scenarios. This review thus represented recent development on the GDY modifications and the corresponding functionalities of alkyne bonds.The precise modifications of graphdiyne (GDY) with the unique acetylene rich structure can be summarized as follows: 1) Compounding graphdiyne with nanoparticles (NPs), or the formation of metal graphdiyne bonding to enhance the charge transfer between materials. The structure rich in sp carbon can hybridize with other active components (such as molecules and NPs) to form a larger electron cloud density overlap, resulting in intense interactions. The composition with NPs can accelerate electron transfer and enhance the activity and stability for catalysis. GDY is easy to obtain and lose electrons, which is referred as an “electron sponge” property. A portion of GDY electrons can transfer with the hybrid across the interface. The electron cloud at a polarized region generates unique electron transfer enhancement characteristics.2) Utilizing acetylene bonds as the chemical reaction sites to achieve controlled doping of heteroatoms at desired sites. The sp and sp2 hybrid carbon atoms have a higher chemical activity, providing greater possibilities for the targeted introduction of heteroatoms. Especially, the triple bonds can create a form of nitrogen doping (i.e. sp-N) through pericyclic reaction and click reaction. Some work reveal a clear upward trend with the concentration of sp-N for ORR, OER and CO2RR reaction. Meanwhile, the doping of sp-N atoms with clear chemical sites paves a way for the development of high-performance carbon based catalytic materials via precise site modifications. Furthermore, optimized doping configuration and suitable spatial distance can enhance a catalytic activity when doping multiple elements. These findings clearly demonstrate that GDY can control the doping at desired sites for synergistic effects and catalytic performance optimization.3) The regulation of ions or atoms transportation or anchoring metal atoms. The two-dimensional plane topology of GDY is orderly distributed with molecular pores of specific sizes. The molecular pore and the surrounding acetylene rich structure endow it with a unique localized electron distribution. Therefore, regulating the size of stacking pores and the surrounding environment will affect the mass transfer process, thus applying graphene into more fields like seawater desalination and photothermal steaming evaporation. More importantly, the electrons from alkyne bond can interact with the metal empty orbits. The unique properties of GDY make it a suitable carrier for anchoring single metal atoms. The anchored metal atoms on the surface of GDY tends to be in zero valence, which in turn brings unique catalytic properties.Summary and prospects Graphene is a novel two-dimensional carbon material composed of sp and sp2 hybrid carbon atom topologies. This material has attracted widespread attention in various fields such as materials, chemistry, physics, information, biology, and the environment due to its high conjugation, abundant acetylene bonds, regular ordered pores, and adjustable electronic structure, which still has many challenges and opportunities in the future.1) Developing large-scale, high-quality, and low-cost synthesis technology can provide a solid material foundation for theoretical research and practical applications. The preparation methods for other types of graphene (such as GY, GY-3, and GY-4) are still in the exploratory stage. Obtaining novel graphene materials will expand the application field and clarify the structure-activity relationship.2) The alkyne bonds of graphene provide more designability. Designing chemical reactions based on alkyne bonds is of great significance for improving the performance of non-metallic catalytic materials. Synthesizing graphene and its derivatives with precise structures, controlling the degree of reaction and functionalization of alkyne bonds can effectively expand the scope and depth of “alkyne chemistry”.3) A more precise manipulation of the pore structure of graphene is needed. The precise regulation from molecular pores to nanopores will deepen the understanding of the atoms/ions transport and anchoring in GDY, and fully leverage its structural advantages. Accurately controlling the anchoring points, atomic numbers, and atomic types of metal elements is crucial for developing atomic catalytic materials, enhancing catalytic activity, selectivity and stability.The unique rich alkyne bond and pore structure of graphene provide infinite possibilities for the precise synthesis and controllable preparation. This review can provide a reference to understand the development of graphene materials for various applications.