Scaffold pore size plays a critical role in the infiltration of the cells into the structure. For engineered blood vessels, co-cultures of endothelial (EC) on the lumen, and smooth muscle cells (SMC) on the external surface of tubular scaffolds are performed. The more adequate pore sizes for EC are, in general, smaller than for SMC. In the present work, poly(ε-caprolactone) (PCL) flat film and hollow fibers are prepared by phase inversion. The influence of polymer and coagulation solution compositions on pore morphology of the films is analysed and the results are applied to obtain, in a one step process, PCL hollow fibers with suitable pore size for both EC and SMC.