A high-pressure H2O vapor annealing technique has been applied to nanocrystalline porous silicon (PS). The effects on the photoluminescence (PL) are reported here for PS samples of different initial porosities, in different conditions of the annealing pressure. A drastic enhancement of the PL intensity has been achieved, while both the emission band and the peak wavelength remain almost unchanged. The best results have been obtained with an initial PS porosity of about 68 %. The resulting layers consist of Si nanocrystals embedded into an SiO2 tissue. The high external quantum efficiency obtained in treated PS (23%) may be attributed mainly to a very high surface passivation by high quality oxide and an enhancement in the localization of photoexcited carriers.