Abstract: Fruits are an essential component of the human diet, yet they are highly susceptible to infection by pathogenic microorganisms during postharvest storage and transportation, leading to severe decay and substantial economic losses. While conventional chemical fungicides exhibit remarkable efficacy in disease control, their residues pose environmental and food-safety concerns. In response to growing consumer demand for healthy foods and ecological sustainability, as well as the broader shift toward green agriculture, developing safe, environmentally friendly alternatives has become a research priority. Volatile organic compounds (VOCs) produced by antagonistic microorganisms have emerged as promising fumigant-like, green bio-preservatives owing to their broad-spectrum antimicrobial activity, vapor-phase diffusivity, and environmental compatibility. This review provides a comprehensive overview of common postharvest infectious diseases in fruits, systematically elucidating the concept, types, biosynthetic pathways, and active ingredients of VOCs derived from antagonistic microorganisms, as well as their antimicrobial mechanisms. Additionally, the challenges and strategic applications of VOCs in postharvest fruit preservation are highlighted. By establishing a theoretical framework for VOCs-based natural control technologies, this work seeks to advance the green and sustainable development of postharvest disease management in the fruit industry.