To meet the thermal stability requirement for electro-optic device application, a new hybrid second-order NLO film is successfully prepared from chromophore with aryl-donor and examined by atom force microscope (AFM). The hybrid films exhibites good optical nonlinearity (d33 is 14.1 pm/V). The d33 value of the film has an onset temperature around 115 ℃ and a half-decay temperature at 145 ℃. The distributions of d33 on hybrid films on different substrates are also analyzed after corona poling. The measurement of NLO films on ITO substrates presents some advantages over normal glass substrates.