Nanoporous fibres are advanced materials with wide application in drug delivery, sensor, filtration, membrane, wound dressing, encapsulation and catalysis. Known mechanisms for pore formation in electrospun are temperature-induced phase separation (TIPS) and vapour induced phase separation (VIPS), these are crucial to application and classification. The underestimated factor electrospinning parameter (polymer concentration) resulted in polymer and solvent rich phases which are capable of manipulating orientation in the jet. In view of this, expanded polystyrene was electrospun at various concentration and voltage. The morphology of resultant fibres were examined with Secondary Electron (SE) and Back Scattering Electron (BSE) detectors, both revealed clear porous micrographs. The resultant phases formed during elongation override popular mechanism in the science of pore formation in electrospun fibre. Finally, pathway for polymer re-use in membrane science is presented.