AbstractA series of side‐chain liquid crystalline polymers (side‐chain LCPs) with different flexible spacer lengths and various degrees of crosslinking were synthesized and characterized. The transport properties of O2, N2, CO2 and CH4 in these polymers were measured by using permeation and sorption methods. The values of diffusion and solubility coefficients were found to be significantly affected by the crosslinking reaction. In contrast to conventional crosslinked polymers, the values greatly increase as the degree of crosslinking increases. The reason might be the use of the flexible oligodimethylsiloxane crosslinking agent and the low solubility of gases in the liquid crystalline regions. The transport properties were also demonstrated to depend strongly on the flexible spacer length. This was ascribed to the fact that different liquid crystalline phases are formea. For the smectic phase, the diffusion and solubility coefficients are lower than those found in the nematic one.