Plants use volatile organic compounds (VOCs) to signal and protect themselves in response to biotic and abiotic stresses. These complicated signaling processes involve the emission of VOCs from various plant parts such as flowers, leaves, and roots. VOCs play a dual role in plant defense, both as direct barriers to herbivores and as signaling molecules for indirect defenses, notifying predators and parasitoids. Furthermore, VOCs can function as priming agents, increasing a plant’s defense systems through absorption and conversion into bioactive chemicals. This includes a variety of enzymes and biopolymers with anti-herbivore or anti-pathogen characteristics. VOC-driven techniques in integrated pest management (IPM) have shown potential, with genetically modified plants bred to release certain VOCs that attract natural insect enemies. Moreover, companion or sentinel crops have been employed to manage pests by manipulating herbivore behavior. Understanding the complicated role of VOCs in plant signaling and defense processes will help to better understand ecological interactions and agricultural practices. This review explores the aspects of plant signaling and defense under various biotic and abiotic stresses through the VOCs along with their long-term stress management strategies, shedding light on the possibilities for using VOCs in sustainable agriculture.