Abstract: In order to investigate the influence of polarization conditions on azo-dye molecular orientation in films, azo-dye polymer films of guest-host system were prepared by spin-coating method. The average alignment factor of azo-dye molecules in films were investigated by UV-Vis spectra measured before and after corona poling, as well as second harmonic generation at different corona poling conditions. The experimental results show that the average alignment factor of azo-dye films becomes bigger, and second harmonic intensity first increases and then decreases with the increasing of poling temperature. The closer the poling temperature is to the polymer’s glass transition temperature, the more likely the molecules are orientated. However, PMMA will fall into a state of viscosity at too high