This study reports for the first time the preparation of electrospun microfibrous mat of PIM-EA-TB. The electrospinning was carried out using a chloroform/n-Propyl-lactate (nPL) binary solvent system with different chloroform/nPL ratios, in order to control the morphology of the microfibres. With pure chloroform, porous and dumbbell shape fibers have been obtained whereas with the addition on nPL, circular and thinner fibers have been produced due to the higher boiling point and the higher conductivity of nPL. The electrospinning process conditions have been investigated to evaluate their impact on the fibers morphology. These microfibrous mats presented potential to be used as breathable/waterproof materials, with pore diameter of 11 μm, an Air resistance of 25.10-7 m-1 and water breakthrough pressure of 50 mBar.