Poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) linear triblock copolymer is a thermoplastic elastomer that can be dissolved in different solvents and processed by electrospinning, producing a mat with elastomeric mechanical flexibility that can be interesting for different applications. Understanding and controlling surface properties like hydrophobicity is crucial to obtain a desired performance. Solution characteristics as well as equipment parameters influence the processability, so that in some cases electrospraying takes place and only particles are deposited on the collector. In optimal electrospinning conditions, uniform fibers are obtained. In each case the differences on mat surface roughness reflect on surface properties. In this work, electrospun mats of SEBS were produced by electrospinning using different solvents and processing conditions to evaluate the effect on wetting behavior. The mats were characterized by water contact angle measurements, scanning electron microscopy and image analysis. The effect of voltage, volume flow rate, concentration of solution, type of solvent and relative humidity on mat and individual fiber or particle morphology was evaluated.