The planar orientation of Nematic Liquid crystal (NLC) molecules on the surface of (111) plane of silica photonic structure has been investigated. Nano voids of silica photonic crystal has been obtained by vertical deposition technique on indium tin oxide-coated substrate. NLC was infiltrated into the channels of voids in the photonic structures. Optical texture studies under with and without electric field were applied to investigate the NLC orientation. It is observed that NLC molecules in the nano voids of silica photonic structure exhibit an excellent planar alignment. This obtained hybrid composite structure on infiltration of NLC will be a promising candidate for electro optic applications.