Binary colloidal crystals (see Figure) of large (L) and small (S) silica colloidal spheres with large diameter ratios have been rapidly constructed by stepwise spin-coating. The dominant structure of the resultant crystals is LS2, with which the LS3 structure usually coexists. The diameter ratio and the speed of spin-coating are used to control the structures, with higher spin speeds favoring the formation of LS3 structures.