Electrospun scaffolds of the biodegradable and biocompatible poly-4-hydroxybutyrate (P4HB) polyester have been prepared using horizontal and vertical set-up configurations of electrospinning. Specifically, it has been evaluated the influence of solvent, polymer concentration, and processing parameters, such as applied voltage, flow rate, and needle tip-collector distance. Scaffolds obtained under the most favorable conditions were characterized in terms of crystallinity, lamellar supramolecular order, thermal (including calorimetric and thermogravimetric data), mechanical, and surface properties. Results pointed out significant differences with respect to commercial sutures (based in P4HB, e.g., MonoMax®) and demonstrated that electrospun scaffolds were constituted by crystalline microfibers with a tangled distribution that leads to high modulus Young modulus (4 MPa), maximum strength (28 MPa), and elongation (360%). Furthermore, new scaffolds had thermal stability and a rough surface that led to a hydrophobic character (105°). Scaffolds could also be successfully loaded during the electrospinning process with a peptide analog to the fibroblast growth factor (e.g., CYRSRKYSSWYVALKRC), giving rise to fully biocompatible samples with a clear acceleration in wound healing.