Incorporation of aliphatic units to poly(butylene terephthalate) (PBT) gives rise to biodegradable copolymers with tunable properties (e.g., degradability), depending on the selected comonomer and the specific composition. Specifically, a low molecular weight poly(butylene sebacate-co-terephthalate) (PBSeT) with a high ratio of aliphatic sebacate units (i.e., 70 mol-% with respect to the total dicarboxylate content) has been employed in this work to get new electrospun biodegradable scaffolds. Appropriate electrospinning conditions have been found despite the limited copolymer molecular weight. In addition, PBSeT has been employed to improve biocompatibility and biodegradability of scaffolds based on the PBT homopolymer. Scaffolds with different properties have been prepared following two strategies: Electrospinning of single solutions of PBT and PBSeT mixtures and co-electrospinning of independent PBT and PBSeT solutions. Characterization involved spectroscopic (FTIR, NMR), calorimetric (DSC, TGA) and surface hydrophobicity analyses. Hydrolytic and enzymatic degradation studies demonstrated the success of the approach due to the susceptibility of the PBSeT component towards the enzymatic attack with lipases from Pseudomonas cepacia and even towards high temperature hydrolysis. [Figure not available: see fulltext.]