Aqueous solutions of polyvinyl alcohol (PVA) were electrospun and its characteristics were studied as a function of applied potential, tip-target distance and solution flow rate. Solutions of PVA and chitosan were homogeneously mixed and electrospun to result in blend nanofibres and their properties were investigated. Conditions were revealed under which multiscale bi-modal fibres could be electrospun in a single step, producing structures that have potential applications in tissue engineering. Electrospun fibres having a bimodal size distribution of poly(caprolactone) (PCL) were also fabricated using a modified electrospinning setup. Nanofibrous microporous PVA scaffolds were fabricated using a cryogenic grinding method with subsequent compaction. Such multiscale porous structures would offer ideal matrices for tissue engineering applications.