Green leaf volatiles (GLV) play an important role in the chemical information network among plants, pest insects and natural enemies. That the release disciplines, metabolic pathways and the ecological functions on different biological communities of GLV was systematacially introduced in the paper. Defense-related genes and secondary metabolites can be induced and generated by GLV in plants defense response. GLV itself and HIPVs and extrafloral nectar induced by GLV can both be spreaded as the warning signals between plants, to attract and repel herbivorous insects, to play the role of synergistic and inhibitive effects with insect pheromones, to attract parasitic wasps and also to affect the growth of pathogenic micro-organisms. Although many natural enemies can be apparently allured by GLV in the laboratory conditions, their parasitic and predatory behaviors are easily influenced by background odors, meteorological conditions, population distribution and quantity of insect pests, and many other factors in the field conditions. It is too complicated and difficult to achieve the ideal biological control efficiency. Before indirect defensive functions of herbivore-induced plant volatiles are used as the regulatory measures with the chemical ecology for phytophagous insect populations in fields, many unknown aspects such as chemical genetics and ecology of insect pests, the interaction mechanism among plants, pest insects and natural enemies, the interactions between the control efficiency and different population densities of herbivorous insects in fields, are still needed to do in-depth research in order to determine multiple ecological functions of the key substances of HIPVs and develop application technology in fields.