Poly(epsilon-caprolactone) (PCL) nanofibers and PCL/silica membranes were synthesized by sol-gel derived electrospinning and casting, respectively. Smooth PCL nanofibers were obtained from the precursor containing N,N-climethylformamide (DMF). PCL/silica membranes were prepared by varying the tetraethyl orthosilicate (TEOS) contents from 0 to 40 vol% to investigate the effect of silica addition on mechanical properties and cytotoxicity of the membranes. Although the strength of the membranes decreased from 12 to 8 MPa with increasing the silica content, the strength remained almost constant 7 weeks after dipping in phosphate buffered saline solution (PBS). The strength reduction was attributed to the presence of a patterned surface pores and micro-pores present in the walls between pores. The crystal structure of the membranes was orthorhombic and the crystallite size decreased from 57 to 18 nm with increasing the silica content. From the agar overlay test, the PCL/silica membranes exhibited neither deformation and discoloration nor lysis of L-929 fibroblast cells.