Enhanced photoluminescence (PL) at room temperature from thermally annealed a-Si:H/SiO2 multilayers is observed through the step-by-step thermal post-treatment. The correlation between the PL and the crystallization process is studied using temperature-dependent PL, Raman, cross section high-resolution transmission electron microscopy (X-HRTEM) and x-ray diffraction (XRD) techniques. An intensified PL band around 820 nm is discovered from the sample annealed near the crystallization onset temperature, which is composed of two peaks centred at 773 nm and 863 nm, respectively. It is found that the PL band centred at 863 nm is related to the pseudo nanocrystal (p-nc-Si) silicon, and the PL band centred at 773 nm is attributed to Si = O bonds stabilized in the p-nc-Si surface.