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Recent studies have shown that surface and gaseous contaminant interactions may play an important role in indoor air quality. Modeling is an important tool to improve our knowledge about the phenomena involved and define appropriate ventilation strategies. However, data for sorption isotherms and diffusion in building materials remain woefully lacking. This paper deals with the latter point. It aims at investigating a methodology based on an analysis of the material porosity first and then the application of Carniglia's mathematical model to determine the effective diffusivity of gaseous species in building materials. This methodology, whose main principles are presented in the first part of the paper, was applied to seven commonly found materials. Mercury intrusion porosimetry (MIP) tests, and the calculations using Carniglia's model, reveal typical total porosities and tortuosity factors for these materials. The analysis of pore size distributions (PSDs) also draws one's attention to the possible differences in the pore structures that may exist between two samples of the same type of material and the differences in the effective diffusivities of contaminants that may result from them. The computed effective diffusivities were subsequently compared to data from experiments carried out in the frame of the EC project MATHIS. An agreement was obtained, thus validating Carniglia's methodology - a methodology that offers many practical advantages compared to diffusion-cell methods.