Three microporous spiro-centered poly(benzimidazole) networks were synthesized based on the condensation of di-/trialdehyde with 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5',6,6'-tatrone in refluxing glacial acetic acid containing ammonium acetate. Fourier transform infrared and solid-state cross-polarization/magic-angle-spinning 13C NMR spectroscopy were utilized to confirm the presence of benzimidazole ring in the obtained polymers. The morphology can be observed from scanning electron microscopy and transmission electron microscopy images. The materials possess Brunauer–Emmet–Teller specific surface area ranging from 520 to 600 m<2> g<–1>. The highest hydrogen and carbon dioxide sorption capacity of the obtained poly(benzimidazole) networks are up to 1.60 wt % (77 K and 1.0 bar) and 13.6 wt % (273 K and 1.0 bar), which are comparable with those of most of microporous organic polymers.