Poly(vinylidene fluoride-trifluoroethylene), P(VDF-TrFE), electrospun membranes were obtained from a mixture of dimethylformamide (DMF) and methylethylketone (MEK) solvents. The inclusion of MEK to the solvent system promotes a faster solvent evaporation allowing complete polymer crystallization in the jet traveling between the tip and the grounded collector. The main electrospinning processing parameters were systematically changed to study their influence on fiber dimensions and distribution. Applied voltage and inner needle diameter do not have a large influence on the electrospun fiber average diameter but do on the fiber diameter distribution. On the other hand, increasing the distance between the needle tip and the collector gives origin to fibers with larger average diameter. Independently of the processing conditions, all membranes are produced in the electroactive phase of the polymer. Further, MC-3T3-E1 cell adhesion is not inhibited by the fiber membrane preparation, showing their potential use for biomedical applications.