A hydrophobic hypercrosslinked polymer with poly (4-tert-butylstyrene-styrene-divinylbenzene) matrix (LC-1) was prepared as adsorbent for the removal of volatile organic compounds from gas streams. The content of oxygen-containing functional groups of LC-1 was about one-fourth that of commercial hypercrosslinked polymeric adsorbent (NDA-201). The results of the water vapor adsorption experiment indicated that LC-1 had a more hydrophobic surface than NDA-201. Three chlorinated volatile organic compounds (trichloroethylene, trichloromethane, and 1, 2-dichloroethane) were used to investigate the adsorption characteristics of LC-1 under dry and humid conditions. Equilibrium adsorption data in dry streams showed that LC-1 had good adsorption abilities for three chlorinated VOCs due to its abundant micropore structure. Moreover, the presence of water vapor in the gas stream had negligible effect on breakthrough time of three chlorinated VOCs adsorption onto LC-1 when values of relative humidity were equal to or below 50%; the breakthrough time of three chlorinated VOCs decreased less than 11% even if the relative humidity was 90%. Taken together, it is expected that LC-1 would be a promising adsorbent for the removal of VOCs vapor from the humid gas streams.