A series of polysiloxane side chain liquid crystal polymers with strong polarity cyano substitution-terminated achiral side chains and cholesterol-terminated chiral side chains was successfully synthesized via thiol-ene click chemistry. H-1-NMR, FT-IR, and thermogravimetric analysis were used to confirm their chemical structures and thermal stabilities. Their phase transition behaviors and phase structures were systematically investigated by a combination of analysis methods such as differential scanning calorimetry, polarized optical microscopy, and X-ray. Results revealed that attributing to the decisive role of the polarity interaction, all the polymers only developed a monolayer interdigitated SmA phase in which the period arrangement was determined by the cyano-terminated side chains, the increased content of cholesterol-terminated chiral side chains (X-chol) just expanded the distance between neighboring molecules within a layer. (C) 2017 Wiley Periodicals, Inc.