With the increasingly prominent disadvantages of chemical fungicides, biological control has gradually attracted more attention for controlling disease of postharvest fruits and vegetables. Among biological control agents, volatile organic compounds (VOCs) produced by different microorganisms can significantly inhibit the growth of various pathogens, and effectively control postharvest fruit and vegetable decay. Thus, VOCs synthetized by microorganisms are favored due to their safety, effectiveness, environmental harmlessness, easy degradation and no residue. Therefore, we review here the diversity of microorganisms with the ability to produce VOCs, the diversity of VOCs from microorganisms, the antifungal activities of VOCs and their possible related mechanisms responsible for the biocontrol effect, to provide an basis to develop biocontrol agents.