Obstacles persist in the treatment and prevention of articular cartilage defects. Polycaprolactone (PCL) and poly(vinyl-pyrrolidone) (PVP) biomaterials were obtained by electrospinning and electrospraying to inspect their potential application for cartilage regeneration. Sodium hyaluronate (SH) was then added into nanofibers of PCL and particles of PVP. The aim of incorporating sodium hyaluronate to this polymer is to enhance the capacity of articular cartilage to regenerate. Human bone marrow-derived mesenchymal stem cells (hBM-MSCs) were seeded onto these tissue engineering (TE) products. The cell viability in vitro and the ability of biomaterials to support the chondrogenic differentiation of hBM-MSCs have been assessed. We report here that hBM-MSCs on these biomaterials were not able to regenerate articular cartilage mainly due to unsuitable culture environment.