Cellulose nanocrystals (CNCs) are a green resource which can produce photonic crystal films with structural colors in evaporation-induced self-assembly; CNC photonic crystal films present unique structural colors that cannot be matched by other colored materials. Recently, the mechanisms of CNC photonic crystal films with a unique liquid crystal structure were investigated to obtain homogenous, stable, and even flexible films at a large scale. To clarify the mechanism of colorful CNC photonic crystal films, we briefly summarize the recent advances from the correlations among the preparation methods, microstructures, and color properties. We first discuss the preparation process of CNCs, aiming to realize the green application of resources. Then, the behavior of CNCs in the formation of liquid crystal phases is studied, considering the influence of the CNCs’ size and shape, surface properties, and the types and concentrations of solvents. Finally, the film formation process of CNCs and the control of structural colors during the film formation are summarized, as well as the mechanisms of CNC photonic crystal films with full color. In summary, considering the above factors, obtaining reliable commercial CNC photonic crystal films requires a comprehensive consideration of the subsequent preparation processes starting from the preparation of CNCs.