Poly (3-hydroxybutyrate)(PHB)/poly (epsilon-caprolactone)(PCL)/silica hybrid scaffolds with and without calcium were fabricated through the combination of electrospinning and sal-gel methods. In this paper, the effects of different amounts of silica Sol on the morphology, mechanical and thermal properties of hybrid scaffolds were studied. The results indicated that as the silica content increased to 50 wt%, the ultimate tensile strength and modulus were enhanced to 191% and 614%, respectively. In addition, the presence of silica decreased the elongation at break significantly. Calcium addition changed the morphology of the hybrid scaffolds from relatively dense fibermats to highly fluffy porous structures, which may be due to the ionization of Ca2+ in the polymer solution. Chemical interactions between the different components and the thermal properties were also based on FTIR, DSC and TGA measurements. The addition of inorganic components significantly decreased the crystallinity of PHB and PCL, which was also confirmed by XRD analysis. Due to the intrinsic performance of the biopolymer and inorganic components, the scaffolds in the present study have great potential for tissue engineering applications. (C) 2014 Elsevier Ltd. All rights reserved.