Nanofibers, with their high surface area-to-volume ratio, elasticity, and mechanical strength, significantly enhance scaffold structures for skin tissue engineering. The present study introduces a unique method of combining solution blow spinning (SBS) and freeze casting to fabricate biomimetic hybrid nanofibroporous scaffolds (BHNS) using polycaprolactone (PCL) and chitosan (CH). The developed scaffolds mimic the fibrous porous natural extracellular matrix (ECM) architecture, promoting cell adhesion, proliferation, and matrix deposition. The combined SBS and freeze-casting processes resulted in scaffolds with high porosity and optimal mechanical strength, crucial for effective skin regeneration. Scanning electron microscopy (SEM) confirmed the uniform, nonwoven, and beadless architecture of the PCL fibers and the fibroporous nature of the PCL/CH scaffolds. The scaffolds exhibited excellent swelling behavior, controlled degradation rates, and enhanced mechanical properties. In vitro cell studies demonstrated scaffold cell-supportive properties in terms of cell attachment, proliferation, and migration. This innovative layer-by-layer fabrication technique, integrating nanofibers with freeze-cast scaffolds, represents a significant advancement in skin tissue engineering, promising improved outcomes in wound healing and regenerative medicine.