Photorefractive (PR) composites based on poly(N-vinylcarbozale) and azobenzene have been fabricated. Two beam-coupling and four-wave-mixing phenomena were observed in the absence of an exteal electric field or prepoling. The maximum two-beam-coupling gain coefficient and the refractive index modulation were measured to be 79 cm-1 and 2.2 × 10-4 respectively. The all-optical-PR phenomenon is explained based on the photoassisted poling of the azo dye by the synergism of the photoisomerization and the longitudinal electric field due to longitudinal intensity gradient of writing light beams. The bi-hole-transporting system provides more chargecarrier traps resulting in improvement of PR performance.