Interactions of polymer and solvent in a highly chemical crosslinked polystyrene (PS) and polymethyl acrylate (PMA) gels are investigated. Crystal thermo of the benzene in PS-benzene gels were analyzed using differential scanning calorimeter (DSC). It was noted that benzene molecules in the gels can be categorized into three types, which is free benzene, weak bonded benzene and strong bonded benzene. In average, one PS structure unit interacted with three benzene molecules in the gel system. The conformation of dichloroethane (DCE) in PMA-DCE gels was studied using Fourier transfer infrared (FTIR). In PMA-DCE gels, DCE molecule bonded with PMA chains in a trans mode through a hydrogen bond. And the amount of trans DCE molecules increased with the increase in concentration of PMA in the gel system.