Low molecular weight liquid crystals (LMWLCs), 4-[(4-bromoalkyloxy)-phenylazo]benzonilrile (AZO(n)) series were synthesized. Mesogenic monomers, 4-(4-propenoylalkyloxy)-4’-cyanobiphenyl (MCA) were synthesized and both homopolymer and copolymer with a methyl methacrylate (MMA) unit were prepared by free radical polymerization. Polymer/LMWLC composites (P/LCs) were prepared with LMWLC AZO(6) and AZO(8) and non-mesomorphic SCLCPs, PMCA(6)-3 and PMCA(8)-3, where (6) and (8) represent the number of methylene unit in the spacers of both LMWLC and SCLCP. It was observed that Delta T-g (defined as T-g of polymer-T-g of P/LC) was smaller and Delta T-NI (defined as T-NI of LMWLC-T-NI of P/LC) was larger, respectively in the case of P/LC samples with the same (6/6 and 8/8) spacer length.