A novel nonprecious material was designed via electrospinning and carbonization to fabricate metallic (CoNi/Cr) nanoparticles (NPs)-encapsulated carbon nanofibers (NFs). The as-fabricated NFs were investigated in terms of morphology, crystallinity and surface chemistry through FESEM, TEM, EDX, XRD and XPS measurements. These analyses confirmed that the designed material owned metallic NPs encapsulated in carbon NFs. The introduced material had a rich carbon content on the surface which was due to the use of polyvinyl alcohol as a precursor polymer. Cyclic voltammetry (CV), chronoamperometry (CA) and impedance (EIS) analyses were applied in a three-electrode system to study the efficiency of the fabricated NFs for urea electrooxidation. The synthesized NFs showed superior catalytic behavior in the alkaline medium towards urea oxidation. The high efficiency was found to be at 0.5 M of urea according to the influence of urea and applied potential studies. This superior activity can be due to the assembly of trimetallic system CoNi/Cr encapsulated C-NFs which has rarely been studied before. This study presents the preparation of a novel cheap material to facilitate the urea fuel cell commercialization.