Herein, crack-free photonic crystal templates with enhanced color contrast were first demonstrated by the coassembly of polystyrene (PS) microspheres and graphene oxide (GO). Then, photonic crystal hydrogels (PCHs) with quick responses to temperature and alcohol solution concentration changes were fabricated by photopolymerization of monomers in the gaps of the self-assembled colloidal crystal templates. The structural color of the PCHs changed from yellow to blue within 120 s as the temperature rose from 25 to 40 °C, whereas upon a decrease in temperature from 40 to 25 °C, the structural color changed from blue to yellow. The structural color of the PCHs also shows an obvious response with the concentration of alcohol solution ranging from 40 to 100 wt %. The quick responses of the PCHs' structural color to changes in temperature and alcohol solution concentration are attributed to the temperature sensitivity of poly(N-isopropylacrylamide) and preferential adsorption and swelling of the alcohol solution for the polymer chains. Furthermore, moxifloxacin (Mox) was loaded into PCHs by hydrogel swelling and exhibited sustained released by increasing the temperature. The sustained release process was facilely monitored by observing the corresponding color changes in real time. The rapid and visible response offers the fabricated PCHs great potential application prospects in the semiquantitative analysis of alcohol concentration and intelligent drug delivery.