Poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) linear triblock copolymer is a thermoplastic elastomer composed of immiscible blocks, resulting in an unique microstructure that consists of hard blocks of styrene (S) in a soft matrix of ethylene-co-butylene (EB) blocks. This type of copolymers can have different types of morphology and assume different degrees of orientation depending on the processing technique. In electrospinning, the strong elongational flow caused by electrical force can be a way to obtain aligned morphologies. Additionally, the rapid evaporation of solvent can change the distribution of phase domains and contribute to the formation of nanopores on the fibers’ surface. This porous structure is also influenced by relative humidity during the experiments. In this work, electrospun mats of SEBS were produced by electrospinning using either chloroform/toluene or chloroform/toluene/DMF as the solvent. The effect of voltage, volume flow rate, concentration of solution, and humidity within the chamber on the quality of the mesh and morphology of fibers obtained was evaluated.