Two dimensional electron momentum distributions (EMD) have been mapped by the two-dimensional angular correlation of positron annihilation radiation (2D-ACAR) to study the electronic structure and microstructural characteristics of porous silicon. The open volume defects associated with vacancies and their complexes present in the porous layer have been analysed using the EMD spectra. Also, the correlation between EMD and the pore formation mechanism was studied and the surface properties were analyzed along with the photoluminescence spectra.