This report is an approach to form thin-film solar cells on graphite as an alternative electrode for the development of solar cells toward the next generation. From the early stage of development of CZTS, composing of copper (Cu), zinc (Zn), tin (Sn), and sulfur (S), Mo-coated substrates have been used. However, the definition of rare metals in recent years already includes Mo. We focus the graphite as a bottom electrode and the substrate because of its versatility and inexpensive cost. The CZTS precursor was prepared by the RF sputtering method. After that, NaF was deposited by the E-B vapor deposition method to control the Na composition ratio. CZTS films were obtained by gas-phase sulfurization. CZTS solar cells with MgF2/Al/AZO/CdS/CZTS/Graphite structure were prepared. These results suggest the CZTS on the graphite with NaF control shows the potential for realizing the low cost CZTS solar cell.