Si quantum dots/SiO2 multilayers were prepared by annealing a-Si:H/SiO2 stacked structures at 1100°C . Photo- and electro-luminescence band around 750nm can be observed from Si QDs/SiO2 multilayers due to the recombination of electron-hole pairs in Si QDs/SiO2 interfaces. The electro-luminescence intensity was obviously enhanced after post hydrogen annealing at 400°C. Electron spin resonance measurements were used to characterize the change of the defect states after hydrogen annealing. It is found that there exists a-centers (g value=2.006), which is related to the Si dangling bonds in Si QDs in our samples. Hydrogen annealing can significantly reduce non-luminescent a-centers and enhance the electro-luminescence intensity consequently.