In this study, polyvinylpyrrolidone (PVP) fibers were fabricated using electrospinning, and their properties were enhanced through dual doping with zinc (Zn) and tin (Sn) ions at different Zn:Sn mixing ratios. The structural, optical, and electrical characteristics of the fibers were investigated to evaluate their potential for photodetector applications. The X-ray diffraction (XRD) analysis of pure PVP fibers indicates an amorphous nature, whereas two broad diffraction peaks emerge after mixing with ions, which is caused by the rearrangement of PVP chains due to their interactions with the added ions. Field emission scanning electron microscopy (FESEM) images show a significant reduction in fiber diameters and an increase in the density of the prepared fabric with an increase in the metal ion dopant. Fourier transform infrared (FTIR) analysis revealed shifts and intensity changes in characteristic peaks and the appearance of metal oxide bands, indicating interactions between the polymer matrix and the dopant ions, that contributed to the enhanced functional properties. Incorporating Zn and Sn ions significantly improved the photodetector performance of PVP fiber/n-Si devices. The doping with the two ions significantly enhanced the photocurrent to 12.5 times compared to 2.5 times in the pure PVP fiber/n-Si sample. The fabricated photodetector fibers at a 3:7 metal ion to PVP ratio show a maximum photosensitivity of 24.8% under a violet light source. The results from this study demonstrate the potential of dual Zn and Sn ion-doped PVP fibers as efficient, low-cost, and flexible materials for photodetector applications to violet light.