Palladium(0) (Pd) and copper(I) oxide (Cu2O) nanoparticles (NPs) were successfully embedded in electrospun polyvinylpyrrolidone (PVP) fibrous membranes. The fabrication process involved the synthesis of stable, PVP-capped Pd and Cu2O colloidal hybrid solutions in methanol that on subsequent electrospinning afforded PVP-Pd and PVP-Cu2O fibrous mats. The morphology of the as-prepared nanocomposite fibers was characterised using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM revealed the presence of bead-free, cylindrical fibers with diameters in the submicrometer range while TEM revealed the presence of spherical Pd and Cu2O NPs with diameters below 10 nm that were evenly distributed within the fibers. Thermal treatment of the PVP-Pd and the PVP-Cu2O membranes afforded crosslinked fibrous mats as supported by SEM. Furthermore, the presence of homogeneously distributed Pd and Cu2O NPs within the crosslinked polymer fibers was confirmed by HRTEM/EDX analyses. The above-mentioned nanocomposite fibers demonstrated high catalytic efficacy as heterogeneous catalytic supports in Heck, Suzuki (PVP-Pd) and click (PVP-Cu2O) reactions. Finally, the reusability of the membranes was briefly investigated with up to three consecutive runs being effective.