For the multifunctional liquid crystalline medium with high chromophore content, a thermotropic polymethacrylate (PBBS) bearing monolithic photoactive mesogen was designed and synthesized on the basis of semiempirical quantum calculation. PBBS showed phase transition sequence of I-222 degreesC-SmA-169 degreesC-SmC-154 degreesC-SmX on cooling. Phase transition in the PBBS film:could be correlated with the birefringence change and II-aggregate formation monitored as st function of temperature. The multifunctional mesogenic pendant, 2-biphenyl-5-sulfonylbenzoxazole, provided strong blue fluorescence and electroluminescence, large second-order optical nonlinearity, and intrinsic photoconductivity to the novel photoactive liquid crystalline polymer PBBS: