Two kinds of stable colloidal crystals have been prepared from polymeric or SiO2 colloids in the presence of diazoresin (DR) as a thermosetting agent combining thermal treatment. Following the decomposition of -N-2(+) groups of DR under heating, the ionic bonds between the DR molecules and colloids change to covalent bonds and the colloidal crystals become very stable toward ultrasonic washing. The colloids were then removed by tetrahydrofuran (THF) in the case of organics or by hydrofluoric acid (HF) for the inorganics to leave the macroporous DR materials.