Blinking fluorophore perovskite nanocrystals (NCs) were employed to image the fine structure of the polystyrene (PS) electrospun fibers. The conditions of CsPbBr₃ NCs embedded and dispersed into PS were investigated and optimized. The stochastic optical reconstruction microscopy is employed to visualize the fine structure of the resulted CsPbBr₃@PS electrospun fibers at sub-diffraction limit. The determined resolution in the reconstructed nanoscopic image is around 25.5 nm, which is much narrower than that of conventional fluorescence image. The complex reticulation and multicompartment in bead sub-diffraction-limited structures of CsPbBr₃@PS electrospun fibers were successfully mapped with the help of the stochastic blinking properties of CsPbBr₃ NCs. This work demonstrated the potential applications of CsPbBr₃ perovskite NCs in super-resolution fluorescence imaging to reconstruct the sub-diffraction-limited features of polymeric material.