Reactions of Ta(NMe2)5 and n-propylamine are shown to be an effective system for sol-gel processing of Ta3N5. Ordered macroporous films of Ta3N5 on silica substrates have been prepared by infiltration of such a sol into close-packed sacrificial templates of cross-linked 500 nm polystyrene spheres followed by pyrolysis under ammonia to remove the template and crystallize the Ta3N5. Templates with long-range order were produced by controlled humidity evaporation. Pyrolysis of a sol-infiltrated template at 600 C removes the polystyrene but does not crystallize Ta3N5, and X-ray diffraction shows nanocrystalline TaN plus amorphous material. Heating at 700 C crystallizes Ta3N5 while retaining a high degree of pore ordering, whereas at 800 C porous films with a complete loss of order are obtained. © 2013 American Chemical Society.