Permanent all-optical poling of a side-chain polyimide film with azobenzene chromophore using a low power nanosecond laser was experimentally demonstrated. The characteristic kinetics of growth and decay of the induced second-order susceptibility were measured by second-harmonic generation. The second-order nonlinear optical coefficient d 3 3 was determined to be 2.6 pm/V, and was observed to be stable at 85°C.