The interaction of electrospun mats with water is critical for many possible applications, and the water contact angle on the surface is the parameter usually measured to characterize wetting. Although useful for hydrophobic surfaces, this approach is limited for hydrophilic mats, where wicking also has to be considered. In this case, it is still unclear how the fiber surface chemical composition and morphology will affect the wetting behavior of electrospun mats. In this work, wetting was studied with different hydrophilic membranes produced by blending thermoplastic elastomer poly(styrene)-b-poly(ethylene-butylene)-b-poly(styrene) (SEBS) with amphiphilic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) molecules. Three different types of PEO-PPO-PEO, with different molar masses, PEO content, and physical form were used. The effect of these differences on the wetting behavior of the electrospun mats was evaluated by contact angle goniometry, wicking measurements, and different imaging techniques. X-ray photoelectron spectroscopy was used to characterize the surface chemical composition. The smaller molecules quickly saturated the surface at low concentrations, making the mats hydrophilic. The sheath of PEO-PPO-PEO also resulted in fast absorption of water, when comparing the saturated and nonsaturated surfaces. Longer PEO chain-ends seemed to hinder complete segregation and also led to a higher activation time when in contact with water. Liquid PEO-PPO-PEO was easily leached by water.