In the present investigation, kesterite Cu2ZnSnS4 (CZTS) nanofibers were obtained by electrospinning process using polyvinylpyrrolidone (PVP) and cellulose acetate (CA) solvent separately. The synthesized CZTS nanofibers were characterized using thermogravimetric analysis (TGA), optical absorption, X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), micro-Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS). Our results showed that the PVP synthesized CZTS nanofibers are a single crystalline while CA assisted CZTS nanofibers are polycrystalline in nature. The optical properties demonstrated that the prepared nanofibers have strong absorption in 300-550 nm range with band gap energy of 1.5 eV. The X-ray and micro-Raman analysis revealed that synthesised nanofibers showing pure phase kesterite CZTS. Further the synthesized CZTS nanofibers were used as counter electrodes for dye-sensitized solar cells (DSSCs). Our results indicate that, PVP-CZTS and CA-CZTS counter electrode based DSSC shows 3.10% and 3.90% respectively. The detailed interfaces of these counter electrodes and DSSCs were analyzed by electrochemical impedance spectroscopic (EIS) measurements for analysis of such high power conversion efficiency. The present study will be helpful for alternative counter electrode for Pt counter electrodes in DSSCs application. We believe that our synthetic method will be helpful for low-cost and efficient thin film photovoltaic technology.