AbstractPolymer blends containing liquid crystalline cellulose derivatives potentially enable the fabrication of optical functional materials because of their unique optical properties, that is, structural color and circular dichroism. However, studies on the effect of the compatibility of the components on the optical properties of such blends are scarce, even though component compatibility is a crucial factor for the physical properties of the polymer blends. In this study, we investigated the effect of the component compatibility on the structural color property of binary blends of acetylated hydroxypropyl celluloses (AHPCs) with different degrees of acetylation (DSAc). The spectroscopic analyses of the AHPC blends revealed that the structural color of blends with a small DSAc gap between AHPC components systematically changed with the blend composition, whereas the color of blends with a large DSAc gap was independent of the composition. Compatibility tests via spin–lattice relaxation time measurements using solid‐state nuclear magnetic resonance indicated that the different composition dependence of the color was attributed to the compatibility of the components, which varied according to the DSAc gap.