Three-dimensional ordered porous materials known as inverse opal films (IOFs) were synthesized using nanocrystals with precisely defined morphologies. Comprehensive theoretical and experimental studies of the volume fraction ratio and electrostatic interactions between nanocrystals and polystyrene templating particles enabled the formation of highly ordered crack-free photonic structures. The synthetic strategy was first demonstrated using titanium dioxide (TiO2) nanocrystals of different shapes and then generalized to assemble nanocrystals of other functional materials, such as indium tin oxide and zinc-doped ferrite. Tunable photocatalytic activity of the TiO2 IOFs, modulated through the choice of the shape of TiO2 nanocrystals in conjunction with selecting desired macroscopic features of the IOF, was further explored. In particular, enhanced activity is observed for crack-free, highly ordered IOFs whose photonic properties can improve light absorption via the slow light effect. This study opens new opportunities in designing multi-length-scale porous nanoarchitectures having enhanced performance in a variety of applications.