Polyaniline (PANI) was obtained by in situ polymerization in a polystyrene sulfonic acid (PSS) solution. We prepared a series of PANI/PSS blends with molar ratio of 1:2, and PSS sulfonated at the degrees of 13 mol%, 21 mol% and 30 mol%. A control sample of polystyrene, at an intermediate sulfonation degree of 21%, without polyaniline, was also considered. The impedance spectroscopy, scanning electron microscopy and X-ray diffraction of the blends were evaluated. Increasing sulfonation degree increases the conductivity of the blends. Scanning electron microscopy (SEM) images allowed us to correlate the electrical properties of the blends with their morphologic characteristics. The smoothness of the blends surface observed by SEM increased with the sulfonation degree. X-ray diffraction indicated the increasing order with the sulfonation. This can be associated with homogeneous phase distribution, which results in highly conductive material.