Poly(caprolactone) (PCL) is one of biodegradable and biocompatible polymers, which have received significant attention because they are environmentally friendly and are extensively used in biomedical applications. Electrospinning was a straightforward method to produce nanofibers from polymer solutions in a wide submicron range around 100 nm. However, no clear standard had been established for judging whether a solvent of high solubility for a polymer would produce a solution good for electrospinning. Considering the above-mentioned cause, we explored the effect of solvent on fibrous morphology, FT–IR spectra and 1H NMR spectra, viscosity and shearing strength, differential scanning calorimetry (DSC) of PCL electrospun nonwoven membranes in this article. When NMP and AC were used as the solvent for PCL electrospinning, all of them were composed of smooth and nanosized fibers with similar fiber surface morphologies. Meanwhile, when DCM and CF were used as solvent, there were lots of holes in fibers due to high evaporation. The electrospinnability was good when CA was chosen as solvent due to its lowest viscosity.