Inspired by iridescent color in natural creations, cellulose nanocrystal (CNC) photonic crystals artificially created by nanotechnology have great application prospects due to their potential to control light propagation in the linear and nonlinear regimes. One of the most important development directions of photonic crystals is the diversification of colors, usually by adjusting the pitch. However, few researchers notice the effect of polymer molecular weight and content on pitch regulation and the interaction between polymer and CNC liquid crystals. Polyethylene glycol (PEG) were used as polymers to regulate the pitch of CNC photonic crystals and investigate the changes in microstructure, crystal structure, thermal properties, and liquid crystal texture of the composites by changing the PEG content and molecular weight. Different photonic crystal construction systems show that when the molecular weight of PEG is 0.4 k, it can be filled between CNCs to regulate the pitch of photonic crystals, while when the molecular weight of PEG is 20 k, it cannot always be filled between CNCs in evaporation-induced self-assembly (EISA) process due to the depletion interaction, which cannot effectively regulate the pitch. This study reveals the relationship between PEG and CNC liquid crystals, which supports the development of photonic crystals and the pitch regulation.