A novel photoresponding ionic complex (PANDAZO) was prepared by the ionic self-assembly (ISA) of sodium polyacrylate (PANa) and azobenzene chromophores (NDAZO). The ionic complex forms an interdigitated lamellar structure with full overlap of the side chains. The optical anisotropy was investigated by using a polarization pulse laser (355 nm). Furthermore, a high photoinduced birefringence (螖n = 0.365) was measured by using a continuous 488 nm laser as the pump light.