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Photoluminescence (PL) decay for as‐prepared and dry‐oxidized porous Si following by a nitrogen pulse laser excitation is reported. The PL decay of both samples is nonexponential. For the as‐prepared samples, the PL lifetime decreases from 200 to 60 μs as the PL emission energy increases from 1.55 to 1.90 eV. The spread in values can be interpreted in terms of nonradiative tunneling of carriers between Si microcrystals. For the dry‐oxidized samples, the PL lifetime depends little on the emission energy, and is about 100 μs. On the basis of these results, we conclude that photoluminescence cannot be explained by the tunneling model alone, suggesting that luminescence centers play a role in determining the PL mechanism of porous Si.