Fine polymeric fibers have been gaining interest from the energy harvesting/storage, tissue, and bioengineering industries because of advantages such as the small diameter, high porosity, permeability, and similarities to a natural extracellular matrix. Electrospinning is one of the most popular methods used to fabricate polymeric fibers because it is not as limited in regards to the materials selection, and it does not require expensive or complex equipment. However, electrospun fibers have a severe aerodynamic instability because the small diameter fibers are able to pass through the atmospheric layer when there is a high electric field. As a result, electrospun fibrous mats have serious difficulties with controlling its shape and geometric properties. In this study, a hybrid nano/microfibrous mat is presented that is fabricated using electrospinning with two different solvent-based PCL solutions. This provides control of the fiber diameter, mat porosity, and mechanical properties. Various hybrid fibrous mats were fabricated after an experimental investigation of the effects of solvent on fiber diameter. It was then demonstrated that the mechanical properties and porosity of the fabricated various hybrid mats could be successfully controlled.