This work addresses the challenge to produce fibers from the water-soluble polymer poly(vinyl alcohol) (PVA), using solution blow spinning (SBS) with forced solvent evaporation at the point of fiber formation. PVA at two different molecular weights, with different degrees of acetylation, were successfully blow spun into nano- and micro-fiber membranes, across a range of concentrations in water (12–20 w/v%). Fiber spinnability, morphology and size are correlated to precursor solution viscosity and PVA type. PVA with degree of polymerization 1100 and degree of hydrolysis 98–99% was relatively facile to spin into fibers. Difficulties in spinning high molecular weight PVA were overcome by introducing hot air at the point of fiber formation to force water evaporation. The procedure developed here opens SBS to other aqueous-based polymer and composite systems for environmentally benign fiber and membrane formation.