We firstly demonstrate the synthesis of Cu2ZnSnSe4-xSx (CZTSeS) nanofibers through versatile electrospinning technique. Polyacrylonitrile (PAN) was used as templating polymer that leads to decrease in imperfections on crystal fibers and yields outstanding structure including a few defects with diameter around 250 nm. Sulfurization and/or selenization processes were carried out separately and simultaneously depending upon the demanded chemical structure. Detailed characterization and electrochemical response indicate their potential application for solar cells as p-type semiconductors.