Covalent organic frameworks (COFs) are one class of porous materials with permanent porosity and regular channels, and have a covalent bond structure. Due to their interesting characteristics, COFs have exhibited diverse potential applications in many fields. However, some applications require the frameworks to possess high structural stability, excellent crystallinity, and suitable pore size. COFs based on β-ketoenamine and imines are prepared through the irreversible enol-to-keto tautomerization. These materials have high crystallinity and exhibit high stability in boiling water, with strong resistance to acids and bases, resulting in various possible applications. In this review, we first summarize the preparation methods for COFs based on β-ketoenamine, in the form of powders, films and foams. Then, the effects of different synthetic methods on the crystallinity and pore structure of COFs based on β-ketoenamine are analyzed and compared. The relationship between structures and different applications including fluorescence sensors, energy storage, photocatalysis, electrocatalysis, batteries and proton conduction are carefully summarized. Finally, the potential applications, large-scale industrial preparation and challenges in the future are presented.