Cholesteric liquid crystal polymer network (CLCN) films with a single reflection band have found applications for decoration and anticounterfeiting. The CLCN films with double reflection bands were more suitable for these applications. Herein, they were prepared by using thermochromic cholesteric liquid crystals (CLCs) through a twostep photopolymerization approach. At the first step, due to oxygen inhibition, the CLC monomers near the substrate surface were polymerized at a certain temperature. At the second step, those near the air were polymerized at another temperature. The wavelengths of these two reflection bands of the CLCN film were dominated by the two polymerization temperatures. Based on this approach, patterns with composite colors were prepared, which were suitably applied for decoration. Moreover, a double-layered CLCN film with a broad reflection band was prepared that could potentially be applied for displays.