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We presented fluorescence spectra and cathode-luminescence spectra of as-prepared porous silicon under different preparation conditions. The luminescence of porous silicon may be related to the luminescent centers on porous silicon surface. The luminescent efficiency depended on the porosity of porous silicon, which further depended on the oxidative level of porous silicon with metal assistance. Under back illumination, the higher the oxidative degree of the metal is, the higher is the porosity and the luminescent efficiency of porous silicon. But under front illumination, the results exhibited an opposite tendency, which can be explained by the formation theory of PS.