Silicon oxycarbide (SiOC) fibers with different chemical compositions were successfully fabricated by electrospinning a mixture of polyvinylpyrrolidone (PVP) and commercially available polymethylsilsesquioxane (MK) or polymethylphenylsilsesquioxane (H44) preceramic polymers, followed by cross-linking and pyrolysis at 1000°C in Argon. The influence of the processing procedure (solvent selection, cross-linking catalyst and additives) on the morphology of the produced fibers was investigated. For the MK/isopropanol system, the introduction of 20 vol% N,N-dimethylformamide (DMF) enabled to decrease the diameter of the as-spun fibers from 2.72 ± 0.12 μm to 1.65 ± 0.09 μm. For the H44/DMF systems, beads-free fibers were obtained by adding 50 vol% choloroform. After pyrolysis, the resultant SiOC fibers derived from MK and H44 resins possessed uniform morphology, with an average diameter of 0.97 ± 0.07 μm and 1.07 ± 0.08 μm, respectively. Due to their different chemical compositions, the MK-derived and H44-derived SiOC ceramic fibers could find different potential applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39836.