To construct secondary processes of multiscale architecturing, wrinkly silica microspheres (WSMs) are nested into the empty chamber of templated macroporous structure by using core-shell microspheres to self-assemble the colloidal crystal template and selectively removing the shells. It is a universal approach to form the binary inverse opal (IO) structures and maintain interconnected nanochannels. With gold nanoparticles loaded on the WSMs (denoted Au-WSMs@IO SiO2) in the meantime, it has been demonstrated by the reduction of 4-nitrophenol (4-NP) that the binary IO materials (Au-WSMs@IO SiO2) exhibited higher catalytic efficiency than simple nested microspheres (Au-WSMs) after recycling 15 times. Furthermore, it was nice to see it had excellent catalytic effect in the epoxidation of styrene. Owing to the outstanding catalytic activity, recyclability and mechanical stability of the binary IO materials, it will be a promising way to widely apply in heterogeneous catalysis.