Poly(epsilon-caprolactone) (PCL) has been widely investigated for tissue engineering applications because of its good biocompatibility, biodegradability, and mechanical properties; however hydrophobic nature of PCL has been a colossal obstacle toward achieving scaffolds which offer satisfactory cell attachment and proliferation. To produce highly hydrophilic electrospun fibers, PCL was blended with pluronic P123 (P123) and the resulted electrospun scaffolds physiochemical characteristics such as fiber morphology, thermal behavior, crystalline structure, mechanical properties, and wettability were investigated. Moreover molecular dynamic (MD) simulation was assigned to evaluate the blended and neat PCL/water interactions. Presence of P123 at the surface of electrospun blended fibers was detected using ATR-FTIR analysis. P123 effectiveness in improving the hydrophilicity of the scaffolds was demonstrated by water contact angel which experienced a sharp decrease from 132 degrees corresponding to the neat PCL to almost 0 degrees for all blended samples. Also a steady increase in water uptake ratio was observed for blended fibers as P123 content increased. The 90/10 blend ratio had the maximum tensile strength, elongation at break and crystallinity percentage. Therefore 90/10 blend ratio of PCL/P123 can balance the mechanical properties and bulk hydrophilicity of the resulted electrospun scaffold and would be a promising candidate for tissue engineering application. (c) 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43345.