The structure of the electronic energy levels of a single phase Cu2ZnSnS4 film, as confirmed by Raman Scattering and x-ray diffraction, is investigated through a dependence on the excitation power of the photoluminescence (PL). The behavior of the observed asymmetric band, with a peak energy at ∼1.22 eV, is compared with two theoretical models: (i) fluctuating potentials and (ii) donor-acceptor pair transitions. It is shown that the radiative recombination channels in the Cu-poor film are strongly influenced by tail states in the bandgap as a consequence of a heavy doping and compensation levels. The contribution of the PL for the evaluation of secondary phases is also highlighted.