Tissue engineering (TE) holds an enormous potential to develop functional scaffolds resembling the structural organization of native tissues, to improve or replace biological functions and prevent organ transplantation. Amongst the many scaffolding techniques, electrospinning has gained widespread interest because of its outstanding features that enable the production of non-woven fibrous structures with a dimensional organization similar to the extracellular matrix. Various polymers can be electrospun in the form of three-dimensional scaffolds. However, very few are successfully processed using environmentally friendly solvents; poly(vinyl alcohol) (PVA) is one of those. PVA has been investigated for TE scaffolding production due to its excellent biocompatibility, biodegradability, chemo-thermal stability, mechanical performance and, most importantly, because of its ability to be dissolved in aqueous solutions. Here, a complete overview of the applications and recent advances in PVA-based electrospun nanofibrous scaffolds fabrication is provided. The most important achievements in bone, cartilage, skin, vascular, neural and corneal biomedicine, using PVA as a base substrate, are highlighted. Additionally, general concepts concerning the electrospinning technique, the stability of PVA when processed, and crosslinking alternatives to glutaraldehyde are as well reviewed.