The syntheses of novel side-chain liquid crystalline polyacrylates (LCPAs) containing siloxane spacers were carried out according to a convenient route by preparing alcohol compounds having a mesogenic group linked with a siloxane bond as key intermediates of the monomers. A relatively large mesogenic group was necessary to exhibit a mesophase in this system. The introduction of a siloxane spacer lowered the temperature range of mesophase of LCPAs resulting from the decrease of T, as compared with the corresponding LCPAs containing an alkylene spacer. It was also revealed that the chemical structure of spacer component played an important role for the assembly structure in the mesophase. g