A series of hyper-crosslinked polymers (HCPs) with connected hierarchical porous structures were synthesized from phenyl-based precursors of benzene (BEN), benzyl alcohol, aniline, biphenyl, and 1,3,5-triphenylbenzene (TPB) via the knitting method. The porous structures of the HCPs were greatly influenced by substituent groups and BEN ring number in the precursors. HCPs prepared from TPB had the largest surface area and pore volume with multiscale porosity. The porous structure of the HCPs could also be adjusted by the crosslinker amount. Insufficient crosslinking led to incomplete pore architecture, while excessive crosslinking resulted in a considerable decrease in the pore volume. With these HCPs as adsorbents, the BEN yield in the cigarette smoke could be largely reduced due to the connected multiscale porosity and π–π aromatic stacking interaction that facilitated the smoke aerosol passing and the small aromatic molecules absorbing, showing great potential of these HCPs as adsorbents for effective removal of BEN from cigarette smoke.
