Poly(vinyl alcohol) is one of the most attractive polymers with a wide range of uses because of its water solubility, biocompatibility, low toxicity, good mechanical properties, and relatively low cost. This review article focuses on recent advances in poly(vinyl alcohol) electrospinning and summarizes parameters of the process (voltage, distance, flow rate, and collector), solution (molecular weight and concentration), and ambient (humidity and temperature) in order to comprehend the influence on the structural, mechanical, and chemical properties of poly(vinyl alcohol)-based electrospun matrices. The importance of poly(vinyl alcohol) electrospinning in biomedical applications is emphasized by exploring a literature review on biomedical applications including wound dressings, drug delivery, tissue engineering, and biosensors. The study also highlights a new promising area of particles formation through the electrospraying of poly(vinyl alcohol). The limitations and advantages of working with different poly(vinyl alcohol) matrices are reviewed, and some recommendations for the future are made to advance this field of study.