In this paper, we show a simple biomimetic approach for fabricating thermally stable porous films with multilayered structures by mimicking beetle wings. Honeycomb-patterned porous films (honeycomb films) of poly(1,2-butadiene) (PB) were successfully prepared by casting chloroform solution of PB and amphiphilic polymer under humid conditions. After formation of layer-by-layer (LbL) film of poly(amic acid) (PAA), which is a precursor of polyimide, and poly(allylamine hydrochloride) (PAH) onto the surface of PB honeycomb films, PAA was successfully converted to polyimide by chemical imidization. After imidization, the LbL-coated honeycomb films have high thermal stability.