This review article focuses on the recent advances in poly(vinyl alcohol) (PVA) electrospinning, summarizing the parameters of the process (voltage, distance, flow rate, and collector), solution (molecular weight and concentration), and ambient (humidity and temperature) to understand their influence on the structural, mechanical, and chemical properties of PVA-based electrospun matrices. The importance of PVA electrospinning in biomedical applications, such as wound dressings, drug delivery, tissue engineering, and biosensors, is emphasized. The study also highlights a new promising area of particle formation through the electrospraying of PVA. The limitations and advantages of working with different PVA matrices are reviewed, and recommendations for future research are provided to advance this field. The review covers the principles, methods, PVA types, and applications of PVA electrospinning, including the influence of operating parameters, formulation parameters, and ambient conditions on the morphology and properties of PVA nanofibers. The article discusses the impact of voltage, feed rate, tip-to-collector distance, collector design, polymer concentration, viscosity, surface tension, conductivity, solvent, and relative humidity on the electrospinning process. Additionally, it explores the morphology of electrospun PVA materials and their applications in various fields, such as tissue engineering, drug delivery, and biomedical devices.This review article focuses on the recent advances in poly(vinyl alcohol) (PVA) electrospinning, summarizing the parameters of the process (voltage, distance, flow rate, and collector), solution (molecular weight and concentration), and ambient (humidity and temperature) to understand their influence on the structural, mechanical, and chemical properties of PVA-based electrospun matrices. The importance of PVA electrospinning in biomedical applications, such as wound dressings, drug delivery, tissue engineering, and biosensors, is emphasized. The study also highlights a new promising area of particle formation through the electrospraying of PVA. The limitations and advantages of working with different PVA matrices are reviewed, and recommendations for future research are provided to advance this field. The review covers the principles, methods, PVA types, and applications of PVA electrospinning, including the influence of operating parameters, formulation parameters, and ambient conditions on the morphology and properties of PVA nanofibers. The article discusses the impact of voltage, feed rate, tip-to-collector distance, collector design, polymer concentration, viscosity, surface tension, conductivity, solvent, and relative humidity on the electrospinning process. Additionally, it explores the morphology of electrospun PVA materials and their applications in various fields, such as tissue engineering, drug delivery, and biomedical devices.