A kind of hybrid material was synthesized via sol-gel process with PMMA and TEOS as reactants, and 4’-Iodo-4-dimethylaminoazobenzene (IDMA) as nonlinear optical organic chromophore. The second order nonlinear optical properties of hybrid material in thin films were investigated by using All-optical poling technique, and the influences of films thickness, structure and poling temperature on SHG properties were discussed. The experimental results indicated that the absorption spectrum of PMMA/SiO2/IDMA film was wider than the spectrum of PMMA/IDMA film. As a consequence of the experiment, we found that different thickness films had different SHG saturation values, there was an optimum thickness for the films. In addition, the higher the sample temperature is, the smaller the SHG intensity is. We also found that the existence of SiO2 network in the film significantly improved the azo orientation stability.