We synthesized highly porous hypercross-linked polymers of (4, 4′-bis ((chloromethyl)-1, 1′-biphenyl-benzyl chloride)) [designated as HCP-BCMB] and (1, 3, 5-triphenyl benzene-1, 4-bis (chloromethyl) benzene) [designated as HCP-TPB] as sorbents for the removal of volatile organic compounds such as chloroform, toluene and ethyl methyl ketone under humidified conditions. The micro-porous nature of the hypercross-linked polymers (pore diameter 0.8nm) was confirmed by Brunner–Emmet–Teller (BET) and scanning electron microscopy (SEM) techniques. HCP-TPB showed a maximum adsorption of 32.8 wt% for toluene. In addition, both the HCPs exhibited CO2 adsorption close to 6 wt% at 25°C and 1atm.