In this study, we present an atomistic simulation study of several structure-property relationships of hypercrosslinked polymers (HCPs) synthesized using styrene (STR), vinylbenzyl chloride (VBC), and divinylbenzene (DVB). Molecular simulation samples were prepared using a virtual polymerization algorithm, Polymatic, with DVB contents ranging from 0 to 50 mol%. The HCP polymerization algorithm and the models were validated by comparison with experimental data: BET surface area, pore volume, H-2 and CO2 loading in 2% DVB samples. Furthermore, the simulated trends in BET surface area and pore volume were in good agreement with the experimental data; both surface areas and pore volumes increased with increased VBC-DVB crosslinking. The same virtual polymerization approach was utilized to study the effect of DVB on the structure and thermodynamic properties of HCPs. Our results demonstrate that DVB mol% significantly altered the structural and gas (H-2 and CO2) adsorption properties of the sample. Finally, though our data demonstrated that structural properties can be tuned at the atomistic level by varying the DVB mol%, they did not exhibit a significant improvement in the performance of H-2/CO2 gas separation applications. (C) 2016 Elsevier Ltd. All rights reserved.