This paper presents results obtained for characterization of porous silicon (PS) layers having different nanostructures, and the influence of this parameter on moisture sensor performances. Two PS layers have been studied, both present the same porosity of 45% and differ in their specific area: 330 m²/g for PS 1 and 223 m²/g for PS 2 . Sorption isotherms were measured; the results justify the use of adsorption theories used to characterize mesoporous materials. Average values of pore diameter computed from adsorption theories and images processing show that PS 1 presents smaller pores than PS 2 . Pore size distributions have been estimated, showing the wider distribution of PS 2 compared with PS 1 . We measured resistivity of PS layers as a function of relative humidity (RH). We found that PS 1 presents higher resistivity and higher relative variation of resistivity. Exposed to moisture step, PS 1 sensor presents faster response time, showing a second advantage among performances criteria.