Surface enlargement and membrane properties have major impact on the use of materials in biological environment, e.g. for filtration, coating or wound dressing applications. This study shows the feasibility of a process combining advantages of room temperature vulcanizing silicone elastomers with the fibrous morphology achieved by an electrospinning process. Using a silicone-acetone-dilution and a heated collector, a stable process could be adjusted and first membranes were spun. Further analytics concerning morphology, hydrophobicity and protein adsorption have been evaluated. Uniform fiber membranes were spun, which show no difference in their wetting behavior compared to the film material. Due to their superior surface-to-volume ratio the spun membranes also offer a higher potential for protein adsorption. © Springer International Publishing Switzerland 2015.