We compare the optically active sub-bandgap states in polycrystalline Cu2ZnSnSe4 (CZTSe) and Cu2ZnSnS4 (CZTS) thin films as a function of sodium content. In all samples studied, we find that CZTSe has a lower concentration of radiative defect-derived states compared to CZTS and that the states are also shallower in CZTSe compared to CZTS. Further, we find that sodium impacts the relative ratios of two sub-bandgap peaks in the 4 K photoluminescence (PL) spectra of CZTSe (one at ∼0.85 eV and another at ∼0.92 eV). We propose that both of these sub-bandgap peaks stem from intrinsic point defects in CZTSe rather than from electronic states introduced by sodium; this is supported by a measurement on a sodium-free single-crystal of CZTSe. We also show that films with stronger emission through the shallower sub-bandgap states at 4 K display room-temperature PL closer to the bandgap energy. For all sodium quantities studied, one broad PL peak is observed in the 4 K PL spectrum of CZTS which also shifts towards the band edge with increasing sodium. A reduced overall defect density and the fact that the states that are present are shallower together may help account for the lower VOC deficits in CZTSe and the empirical observations that sodium improves device performance.