Linear and nonlinear optical properties of electrically poled films of newly synthesized poly [(4′-acetylphenylaminoformyloxy-4-styrene)-co-(4-hydroxystyrene)] [poly(AS-co-HS)] are investigated. Linear optical properties of a poly(AS-co-HS) film are measured by the prism-coupling method. Ultraviolet (UV) transparency down to 350 nm identifies that this polymer is a promising candidate for second-harmonic generation (SHG) in the UV-visible light region. Corona-poling technique is used to produce a noncentrosymmetric structure. The induced d33 at λ=1064 nm is 2.8 pm/V. High glass-transition temperature (Tg=160 °C) results in very long decay time of the nonlinearity, d33. The decay time at operating temperature of 80 °C is estimated to be more than ten years. Guided-mode blue and green SHGs are demonstrated using the film as a slab waveguide. © 2000 American Institute of Physics.