Crosslinked poly(dimethyl siloxane) (PDMS) fibers were fabricated by electrospinning in combination with a sol-gel process followed by heat treatment. Before and after heat treatment, the changes in the chemical and thermal properties of the electrospun PDMS fibers were examined by differential scanning calorimetry (DSC), equilibrium swelling tests, and contact angle measurements. There was no significant change in morphology and average diameter of the as-spun PDMS fibers after heat treatment. The tensile properties of the as-spun PDMS fibers mat increased with increasing heat treatment temperature. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114:3870-3874, 2009