We performed two-dimensional angular correlation of the electron-positron annihilation radiation (2D-ACAR) and positron lifetime measurements on a porous Si sample. From the width of the narrow 2D-ACAR component, attributed to the positronium atom, we estimated the average size of the pores to be ~2.4 nm and did not find evidence of a preferential propagation of the pores. Moreover, by comparing the 2D-ACAR spectrum with that observed for a pure Si crystal, we isolated a further isotropic component attributable to crystal defects of unknown origin.