Metabolomics has emerged as a powerful tool for elucidating the complex biochemical interactions between plants and insects. These interactions involve a diverse array of chemical compounds that mediate defense, communication, and adaptation. Metabolomic profiling enables comprehensive analysis of metabolites involved in these processes, providing valuable insights into the molecular dialogue shaping plant–insect relationships. By examining metabolic changes triggered by insect herbivory or infestation, metabolomics helps identify key defense-related metabolites, including secondary metabolites, phytohormones, and stress-induced enzymes. It also facilitates the detection of insect-derived metabolites that influence plant physiology and modulate host defense mechanisms. Additionally, metabolomics reveals the crucial role of insect gut microbiota in producing bioactive compounds that impact plant–insect dynamics. Comparative metabolomic studies between resistant and susceptible plant genotypes further uncover pathways linked to plant resistance, guiding sustainable pest management and breeding of insect-resistant crops. Integration of metabolomics with genomics and transcriptomics promises to uncover novel defense networks and improve our understanding of plant metabolic plasticity under biotic stress. Overall, metabolomics offers a comprehensive framework for exploring the chemical ecology of plant–insect interactions and holds great potential for advancing knowledge of defense mechanisms and adaptation strategies.