Impacts of annealing and ageing on the photoluminescence（PL） spectra and Fourier Transform Infrared Spectrometry of porous silicon（PS） have been investigated.Deconvolution of the PL spectra into three distinct Gaussian bands reveals that at least two of the bands are relevant to the non-quantum confinement mechanisms.Specifically,it is found that the intensity of the first Gaussian band strongly depends on the Si=O bonds as time prolongs.The intensity of the third Gaussian band may be related to Si-O-Si bonds and SiHx（x=1,2） bonds.The changes of the two Gaussian bands are dependent on annealing temperature.