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A study of the electronic conduction mechanisms and electrically active defects in polycrystalline Sb2Se3 is presented. It is shown that for temperatures above 200 K, the electrical transport is dominated by thermal emission of free holes, ionized from shallow acceptors, over the intergrain potential barriers. In this temperature range, the temperature dependence of the mobility of holes, limited by the intergrain potential barriers, is the main contributor to the observed thermal activation energy of the conductivity of 485 meV. However, at lower temperatures, nearest-neighbor and Mott variable range hopping transport in the bulk of the grains turn into the dominant conduction mechanisms. Important parameters of the electronic structure of the Sb2Se3 thin film such as the average intergrain potential barrier height ϕ = 391 meV, the intergrain trap density Nt = 3.4 × 1011 cm−2, the shallow acceptor ionization energy EA0 = 124 meV, the acceptor density NA = 1 × 1017 cm−3, the net donor density ND = 8.3 × 1016 cm−3, and the compensation ratio k = 0, 79 were determined from the analysis of these measurements. ; P. M. P. Salomé acknowledges the funding of Fundação para Ciencêa e Tecnologia (FCT) through the project IF/00133/ ̂2015. This research is supported by the Development of novel ultrathin solar cell architectures for low-light, low-cost, and flexible optoelectronic devices project (028075) co-funded by FCT and ERDF through COMPETE2020. B. Vermang has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement no. 715027). A. Shongalova acknowledges the funding of Erasmus + program 2016/17. This work was funded by FEDER funds through the COMPETE 2020 Programme and by FCTPortuguese Foundation for Science and Technology under the projects UID/CTM/50025/2013. The financial support from Brazilian funding agencies CNPq, CAPES, and FAPEMIG is also acknowledged. ; info:eu-repo/semantics/publishedVersion