The fabrication of tissue-engineered scaffolds for small-caliber blood vessels still remains a challenge. In the present work, we prepared poly(ε-caprolactone) (PCL) hollow fiber (HF) membranes, suitable for small-diameter blood vessel regeneration, by a phase separation spinning technique. The difficulty of processing PCL, a highly elastic material prone to suffer die swelling by extrusion, was overcome by tailoring the dope solution temperature and extrusion flow rate during the spinning procedure. The influence of the composition of the coagulation bath (water, ethanol, isopropanol) on the HF membrane physico-chemical properties (morphology, transport and mechanical properties) and cell attachment and proliferation was studied. The HF membranes fabricated using ethanol as coagulation bath had the most uniform morphology, good mechanical and transport properties and showed human adipose stem cell attachment and proliferation. Therefore, these fibers are promising scaffolds for small-caliber blood vessel regeneration.