This study addresses the challenge of enhancing the transverse mechanical properties of oriented polyacrylonitrile (PAN) nanofibers, which are known for their excellent longitudinal tensile strength, without significantly compromising their inherent porosity, which is essential for effective filtration. This study explores the effects of doping PAN nanofiber composites with varying concentrations of polyvinyl alcohol (PVA) (0.5%, 1%, and 2%), introduced into the PAN matrix via a dip-coating method. This approach ensured a random distribution of PVA within the nanofiber mat, aiming to leverage the synergistic interactions between PAN fibers and PVA to improve the composite’s overall performance. This synergy is primarily manifested in the structural and functional augmentation of the PAN nanofiber mats through localized PVA agglomerations, thin films between fibers, and coatings on the fibers themselves. Comprehensive evaluation techniques were employed, including scanning electron microscopy (SEM) for morphological insights; transverse and longitudinal mechanical testing; a thermogravimetric analysis (TGA) for thermal stability; and differential scanning calorimetry (DSC) for thermal behavior analyses. Additionally, a finite element method (FEM) analysis was conducted on a numerical simulation of the composite. Using our novel method, the results demonstrated that a minimal concentration of the PVA solution effectively preserved the porosity of the PAN matrix while significantly enhancing its mechanical strength. Moreover, the numerical simulations showed strong agreement with the experimental results, validating the effectiveness of PVA doping in enhancing the mechanical properties of PAN nanofiber mats without sacrificing their functional porosity.