This study reports, for the first time, the fabrication of electrospun Cu2ZnSnS4 (CZTS) nanofibers using metal acetate precursors. Viscous poly(vinyl pyrrolidone) (PVP) solution containing acetate or chloride salts of copper, zinc, and tin was electrospun onto a conductive substrate. The PVP nanofibers that have a mixture of metal salts were annealed at elevated temperatures. After calcination, these nanofibers were treated with the sulfur source and then annealed again in order to generate CZTS nanofibers. The CZTS nanofibers generated from acetate and chloride salts were characterized and compared. Belt-like and wire-like nanofibers were obtained when using metal acetate and chloride precursors, respectively.