Inverse gas chromatographic (IGC) measurements are reported for 17 hydrocarbon probes on a low molar mass hexyloxycyanobiphenyl liquid crystal (LC) mixed with linear poly(dimethyl siloxane) (PDMS). The retention properties are compared with a side-chain liquid crystalline bearing the same mesogen. The results show that the retention of the LC polymer is significantly different from a mixture with the same composition. DSC and IGC values for the transition temperatures indicate that PDMS does not blend with HCB although some interactions, characterised by a Flory-Huggins interaction parameter, were seen and some effect on the liquid crystalline behaviour was noted. The usefulness and limitations of the IGC technique for characterising this type of polymer-LC system are discussed.