Polycaprolactone (PCL) and poly(lactic acid) (PLA) are polymers with unique individual features, but their mixing can produce a new biodegradable material with well‐balanced properties, although with a disadvantage that both are highly hydrophobic materials. To improve this drawback, electrospun PCL/PLA blends with various weight ratios were superficially modified by air plasma. The changes undergone by the nanofibers were characterized using spectroscopic and microscopic techniques; water contact angle (WCA) was also determined. We demonstrated that the electrospun PCL/PLA blends did not suffer morphological changes, although it was observed an increase in the roughness and the O/C ratio (by XPS analysis) and, decrease in WCA values, when the PCL content dominates in the blend after the treatment. The surface characteristics of the scaffolds PCL/PLA blends can be improved after modification with plasma and by tuning the content of its components.