It has been an important trend for searching materials with quicker second harmonic generation (SHG) and some excellent poling conditions. In this paper, the properties of SHG were investigated for spin coating films of the Azo host-guest adulterant dye by using all-optical poling way. The experiment results show that the saturation time of all optical poling was different for the same guest (NBMR) adulterated to different hosts. The poling time of whose hostis PMMA was about 15 min quicker than PA. For the same sample, poling condition Iω/I2ω=9 is better than Iω/I2ω=30. The rule of all-optical poling were basically same for the spin coating films with the same host (PMMA), different guests (NBAR and NBMR) and different thicknesses. The longer of the poling time, the stronger of the SHG intensity during the poling first stageis . But the SHG intensity no longer increases adding when the samples′ SHG intensity reaches a certain saturation value. Then it would be slightly receded with the increasing of poling time, and at last it would reach to a stable value.