The electroluminescence of porous silicon in solutions at positive biases was investigated by luminescence spectrometer. The electroluminescence of porous silicon in solutions mainly depended on its surface properties. The elelctroluminescence was much enhanced when the sample of porous silicon was electrolyzed once again which had undergone an electroluminescence test. The tests of both cyclic voltammetry and the luminescence of the sample of porous silicon prepared by repeated electrolysis provided further evidence that the electroluminescence of porous silicon in solutions at positive biases stemmed from the oxidation of Si-H on the surface of porous silicon. The voltage tunable emitting for porous silicon in formic acid-sodium formate solution at positive biases was revealed, which could be explained with the quantum confinement effect.