Liquid crystals, as an ordered fluid, provide an excellent physical environment for the orderly self-assembly of functional molecules. Traditional research has mainly focused on the one-dimensional ordered assembly of liquid crystal molecules, such as in Nematic or Smectic phases. This article reviews the latest progress in the complex assembly and phase behavior of polyphilic liquid crystal molecules. By regulating the degree and mode of microscopic phase separation, a series of assembly modes have been achieved, ranging from two-dimensional honeycomb columnar phases to three-dimensional network structures. The article explores the influence of steric effects and phase separation on the formation mechanisms of assembled structures, such as superlattices and Frank-Kasper phases, while also analyzing the role of fundamental mathematical concepts like minimal surfaces and supramolecular chirality in assembly behavior. Additionally, it systematically discusses the phase transition paths in two-dimensional tiling of liquid crystals, the control mechanisms of three-dimensional network structures, and the supramolecular chirality behavior arising from symmetry breaking. These studies provide new insights into the understanding of complex supramolecular systems in nature and artificial reticular chemistry.