Nonwoven mats produced by electrospinning present high surface area so that understanding and controlling surface properties like wetting is crucial to obtain a desired performance. Many polymers produce hydrophobic electrospun mats due to a combination of surface chemistry and an increase in surface roughness. However, hydrophilization is needed for many biomedical and environmental applications where there is interaction with aqueous fluids. This can be achieved by a post-treatment of hydrophobic membranes, but with an increase in time and cost. Polymer blending is an attractive alternative to control the surface properties of the mats in a one-step process. In this work, hydrophobic polymers were blended with amphiphilic PEO-PPO-PEO copolymers aiming to control the segregation of this component to the surface. The PPO block tends to segregate to the surface and drag the PEO chain ends. Once in contact with aqueous medium, the PEO segment will extend and hydrophilize the fiber. Also, hydrophilic electrospun mats cannot be seen only as a rough surface, but also as a porous membrane subject to wicking. The mats were characterized by water contact angle and wicking measurements, scanning electron microscopy and image analysis. The effect of chemical composition, mat and fiber surface morphology on the wetting behavior was evaluated.