This work discusses the effect of photo-alignment in a liquid-crystal film that is doped with nanoparticles and azo-dye. The vertical alignment that is induced by nanoparticles of polyhedral oligomeric silsesquioxanes can be changed into homogeneous alignment by the absorption of photo-excited azo-dye. Both electro-optical and surface properties are analyzed to confirm this phenomenon. An electrically tunable polarization-dependent LC phase grating is produced using the method. By this method, we also present a transflective liquid crystal display with a single cell-gap in a dual-alignment configuration. This dual structure was fabricated via a single-step laser-light exposure through a photomask. The vertical alignment induced by nanoparticles of polyhedral oligomeric silsesquioxanes can be changed into a homogeneous alignment via absorption of photo-excited azo dye. The LC molecules at the transmissive and reflective pixels are homogeneous and hybrid alignment, respectively, at which optimal phase retardations of half and quarter wavelengths are achieved. Both nanoparticle- and azo-dye-induced vertical and homogeneous alignments are non-contact alignment processes and have potential for practical application.