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In this work Poly ε-caprolactone (PCL)/ Diglycidyl ether of bisphenol A (DGEBA) blends were electrospun and the obtained mats were UV cured to achieve shape memory properties. In the majority of studies, when blends with different compositions are electrospun, the process variables such as voltage or flow rate are fixed independently of the composition and consequently the quality of the fibers is not optimized in all of the range studied. In the present work, using the design of experiments methodology, flow rate and voltage required to obtain a stable process were evaluated as responses in addition to the fiber diameter and shape memory properties. The results showed that the solution concentration and amount of PCL played an important role in the voltage and flow rate. For the shape memory properties excellent values were achieved and no composition dependence was observed. In the case of fiber diameter, similar results to previous works were observed.