This study investigated gelatin methacryloyl (GelMA) and polycaprolactone (PCL) blend scaffolds incorporating cerium oxide (CeO) nanoparticles at concentrations of 0%, 5%, and 10% via electrospinning for periodontal tissue engineering. The impact of photocrosslinking on these scaffolds was evaluated by comparing crosslinked (C) and non-crosslinked (NC) versions. Methods included Fourier transform infrared spectroscopy (FTIR) for chemical analysis, scanning electron microscopy (SEM) for fiber morphology/diameters, and assessments of swelling capacity, degradation profile, and biomechanical properties. Biological evaluations with alveolar bone-derived mesenchymal stem cells (aBMSCs) and human gingival fibroblasts (HGFs) encompassed tests for cell viability, mineralized nodule deposition (MND), and collagen production (CP). Statistical analysis was performed using Kruskal-Wallis or ANOVA/post-hoc tests (α = 5%). Results indicate that C scaffolds had larger fiber diameters (250 nm) compared with NC scaffolds (150 nm). NC scaffolds exhibited higher swelling capacities than C scaffolds, while both types demonstrated significant mass loss (~50%) after 60 days ( < 0.05). C scaffolds containing CeO showed increased Young's modulus and tensile strength than NC scaffolds. Cells cultured on C scaffolds with 10% CeO exhibited significantly higher metabolic activity (>400%, < 0.05) after 7 days among all groups. Furthermore, CeO-containing scaffolds promoted enhanced MND by aBMSCs (>120%, < 0.05) and increased CP in 5% CeO scaffolds for both variants (>180%, < 0.05). These findings underscore the promising biomechanical properties, biodegradability, cytocompatibility, and enhanced tissue regenerative potential of CeO-loaded GelMA/PCL scaffolds for periodontal applications.