Compared with conventional microporous materials (i.e., zeolites and activated carbon) and advanced metal-organic frameworks, the pursuit of novel microporous organic polymers has been rising rapidly in recent years.In general, the design of rigid, nonplanar, and contorted monomers and highly effective coupling/condensation chemistries should be empirically considered.A series of microporous organic polymers with ketal/acetal linkages were synthesized based on the condensation of aromatic acetyl/formyl monomers with pentaerythritol.