Copper-based quaternary chalcogenide Cu2FeSnS4 (CFTS) is an important material due to its indium-free nature and presence of earth-abundant elements. Herein, CFTS nanofibers have been first fabricated via a facile two-step approach using a simple and inexpensive electrospinning technique. X-ray diffraction and scanning electron microscopy techniques were used to determine structural, morphological, and compositional features of the obtained films. Nanofibers annealed at 500 °C for 1 h were characterized by (112), (200), (220), (312) preferred orientations via X-ray diffraction method. Nanofibers showed well crystallization and tetragonal phase. The average diameters of obtained fibers were found to be 100 ± 50 nm. Cyclic voltammograms showed that CFTS fibers showed p-type behavior.