We proposed a new formation for fibrous mat fabrication from derivatives of polyvinyl alcohol (PVA) and gelatin (Gela) through horseradish peroxidase mediated crosslinking which provides sustain release of methylprednisolone (MP) as a therapeutic approach for SCI regeneration. The polymeric solution of PVA and Gela conjugated with phenolic moieties (PVAPh & GelaPh respectively) containing HRP and MP flowed using a syringe pump in an electrospinning system. The PVAPh/GelaPh fibrous mats were put in air flow saturated with H2O2 which acts as an electron donor and covalently proceed crosslinking of Ph groups in fibrous mats. Implanted scaffolds were then transplanted into the compression SCI rats’ model. A total of 40 rats were injured at the T10-11 level, and regarding transplantation materials. After a specific interval, the animals underwent a study for remyelination and apoptosis using TUNEL and Luxol Fast Blue staining as well as behavioral test. The covalently crosslinked PVAPh/GelaPh fibrous mats were in uniform size distribution without any bead formation and maintained their filament structure. The mechanical properties, hydrophobicity and degradation rate of PVAPh/GelaPh fibrous mat are significantly promoted compared with PVAPh samples and could provide the desired structure for sustain release of MP. The cells adhered, proliferated on this composite which indicates cytocompatibility of resultant PVAPh/GelaPh fibrous mats. Our result showed a significant decrease in apoptotic neurons and a remarkable increase in remyelination in SCI+PVA/GELA+MP group compared to the SCI group. Therefore, the results confirmed the potential of PVA/Gela+MP nanocomposites as a scaffold for SCI through locomotor hind limb function amelioration, neuroinflammation attenuation, improvement of functional recovery and limiting the secondary damages.