Cu2ZnSnSe4 thin films were prepared by using the synthesized Cu2ZnSnSe4 ingot and Na2Se powder at various Na2Se/Cu2ZnSnSe4 mole ratio as evaporation materials for selenization process. From EPMA analysis, the composition was approximately constant even if the Na2Se/Cu2ZnSnSe4 mole ratio increased. X-ray diffraction studies revealed that the thin films had a kesterite Cu2ZnSnSe4 structure and the foreign phases disappeared with increasing the Na2Se/Cu2ZnSnSe4 mole ratio. The Na2Se addition enhanced to grow thin films having a close-packed structure and columnar grains. The values of Voc and Isc in Cu2ZnSnSe4 thin film solar cells increased with increasing the Na2Se/Cu2ZnSnSe4 mole ratio.