The effect of Na incorporation in Cu2ZnSnSe4 (CZTSe) solar cells grown by the coevaporation method was investigated via photoluminescence (PL) and time-resolved PL (TRPL) measurements as well as photovoltaic properties. The TRPL decay curves showed a monotonic increase in CZTSe lifetime from 2 to 15 ns with increasing Na incorporation, which corresponds to the increase in the correction length estimated by quantum efficiency measurements. The TRPL decay curves included two decay components, fast and slow, which were discussed and concluded as originating from the recombination at the surface and bulk of CZTSe, respectively, which is also supported by TPRL measurements with various excitation wavelengths. The lifetime of CZTSe is limited by the surface-related nonradiative recombination compared to Cu(In,Ga)Se2 devices which are fabricated with the same device structure except for the absorber, and at present, it is concluded that the surface recombination of the CZTSe limits the cell performance. In addition to the above investigations, the relationship between the CZTSe bulk lifetime and carrier concentration is discussed; deep nonradiative recombination centers in the CZTSe bulk were found to decrease by one order of magnitude with Na incorporation. The Na incorporation primarily resulted in improvement in the short circuit current density and fill factor and not in the open circuit voltage, and the results are discussed. The best performing CZTSe solar cell with Na incorporation showed a conversion efficiency of 9.57%.