A new liquid-crystal composite, composed of photopolymerizable self-assembled fibers and a smectic liquid crystal, and its photopolymerized composite have been prepared. The fibers oriented along the smectic layers are obtained by self-assembly of an amino acid derivative with terminal methacryloyl groups in the smectic liquid crystal. The oriented fibrous structures are fixed by photopolymerization, resulting in the formation of microgrooves on the substrate surfaces. The aligned direction of the liquid-crystalline molecules is changed to the direction along the fibers after thermal annealing. The patterning of liquid-crystal alignment is achieved for these liquid-crystal composites by patterned photopolymerization.