Low-temperature sulfurization/selenization heat treatment processes for photovoltaic devices are provided. In one aspect, a method for fabricating a photovoltaic device is provided. The method includes the following steps. A substrate is provided that is either (i) formed from an electrically conductive material or (ii) coated with at least one layer of a conductive material. A chalcogenide absorber layer is formed on the substrate. A buffer layer is formed on the absorber layer. A transparent front contact is formed on the buffer layer. The device is contacted with a chalcogen-containing vapor having a sulfur and/or selenium compound under conditions sufficient to improve device performance by filling chalcogen vacancies within the absorber layer or the buffer layer or by passivating one or more of grain boundaries in the absorber layer, an interface between the absorber layer and the buffer layer and an interface between the absorber layer and the substrate.