A study of the electrical conduction mechanisms and electrically active defects in polycrystalline \(Sb_{2}Se_{3}\) is presented. It is shown that at high temperatures the electrical transport is dominated by thermal emission of free holes, ionized from shallow acceptors, over the inter-grain potential barriers. The holes mobility temperature dependence, limited by the inter-grain potential barriers, is the main contributor to the observed conductivity thermal activation energy. At lower temperatures, nearest-neigbour hopping transport in the bulk of the grains is the dominant conduction mechanism. Based in this study important parameters of the electronic structure of the sample such as free hole density and mobility, inter-grain potential barrier height, inter-grain trap density, shallow acceptor ionization energy, acceptor density, net donor density, compensation ratio, and relative dielectric constant are reported.