The requirement for alternative pesticides for agricultural crops has become a public health necessity. By using an ecological approach, we aim to examine how chemical interactions between Taif Pomegranate, Aphis punicae, enemies, and protectors can be tracked in the field. Describe how these substances could be utilized as a powerful crop biocontrol tool to implement integrated pest management (IPM) against A. punicae. Based on insect chemical ecology, volatile organic compounds were collected from four ecological systems: 1) aphid-infested pomegranates (AIP), 2) AIP with ant, 3) AIP with ant and ladybird after 24 h, and 4) AIP with ant and ladybird after 48 h. The composition and quantity of VOCs emitted can result in various responses. The VOC profile of AIP revealed that it is experiencing early injury due to low β-farnesene, methyl salicylate, and high levels of caryophyllene. The main ant pheromone compound, 4-heptanone, can be repellent to aphids by adding ants and ladybirds to AIP for 24 hours. After 48 hours, the key factor in repelling aphids is identified to be as 1-ethyl-3-methylbenzene, 1,3,5-trimethylbenzene, and 1-methyl-1H-imidazole. Meanwhile, methyl salicylate, sabinene, limonene, pentadecane, and heptadecane are found to attract predators. This study's findings will be beneficial for future quantitative investigations that can pinpoint the concentration of every volatile compound required for the biological control of A. punicae.