Melt polycondensation of citric acid (CA) and diols can form biodegradable thermoset bioelastomers with good biological properties and designed performances. However, their cross-linked structure reveals a big challenge to fabricate submicrofibers or nanofibers via electrospinning. Herein, melt polycondensation of CA and 1,8-octanediol in the presence of poly(epsilon-caprolactone) (PCL) was performed to fabricate a prepolymer containing high-molecular-weight poly(1,8-octanediol-co-PCL citrate) (POCL) for facilitating direct electrospinning. The results showed that the direct electrospinning of the prepolymer was still unfeasible even if POCL had a high molecular weight; however, introducing a certain quantity of PCL as carrier polymer realized eletrospinnability and generated fibrous POCL/PCL; the thermal cured POCL/PCL still maintained fibrous structure and was endowed with elastic property; moreover, in comparison with pure PCL fiber mat, they exhibited a better resilience and hydrophilicity.