In this study, electrospinning equipment as a simple and low cost method was used. CaCu₃Ti₄O₁₂ nanofibres were fabricated by a sol–gel electrospinning technique using polyvinylpyrrolidone. To find out the optimum viscosity of the electrospinning solution for obtaining the high quality CaCu₃Ti₄O₁₂ nanofibers, solutions containing different amount of polyvinylpyrrolidone (0.10–0.3 g/ml) were prepared for the electrospinning process. Results indicated that the optimal amount of polyvinylpyrrolidone to be between 0.23 and 0.30 g/ml. The thermal decomposition process, phase structure and morphology of synthesized fibers were characterized by FTIR, DSC-TG, XRD, SEM and TEM. According to results, high purity polycrystalline CaCu₃Ti₄O₁₂ nanofibers with diameters ranging <200 nm were obtained after sintering at 900 °C for 4 h.