This paper reports on photoluminescence (PL), luminescence decay curves, and compositional analysis of porous silicon(PS) which is aged under air ambient by Fourier transform infrared vibrational spectroscopy (FTIR) and by Auger electron spectroscopy (AES). Porous silicos which has been aged under air ambient yields two PL band structures, i.e. blue/violet PL and red PL. The evolution of a blue/violet band is pronounced, especially for thin PS film which is prepared in dilute HF solution. The blue/violet PL band has been observed initially to increrase rapidly with aging, then saturated with further atmospheric aging. The ambient air aged PS exhibits a fast decay time of sub-nanosecond at room temperature and shows appreciably faster decay time than that at 20K. Atmospheric aging of this thin blue/violet luminescing PS yield non-stoichiometric oxide judging from the vibrational spectra of Si-O and AES analysis.