Endoclita signifer is a major wood-boring pest of eucalyptus trees in China, and its third instar larvae can accurately find and infest eucalyptus trees in mixed-species forests, although it can also feed on another 51 tree species in the same planted area. A total of 34 volatile compounds were identified from eucalyptus trunks, including non-infested and infested trunks with single or multiple (more than three) larval entrance cover packets, and forest floor humus. Of these, o-cymene showed a strong gas chromatography-electroantennographic detection (GC-EAD) activity and significant attraction of the third instar E. signifer larvae. Higher abundance of alpha-phellandrene, o-cymene, and the unique 2-phenyl-2-propanol in the volatile profile from infested eucalyptus trunks indicated that they were herbivore-induced plant volatiles (HIPVs). The larvae showed significantly higher attraction to volatile blends, especially those from infested eucalyptus trunks, than to single volatiles. A blend of the three HIPVs, α-pinene, D-limonene, and n-butyl ether may serve as an attractant for the control of E. signifer larvae in eucalyptus plantations. Further, exposure of third instar E. signifer larvae to some of these volatiles which also elicited electroantennogram and behavioral responses, influenced expressions of some olfactory proteins. Our results show that third instar E. signifer larvae can recognize o-cymene from host eucalyptus trunks and are attracted to the trunk by the three HIPVs when they shift their habitats from the forest floor humus to the tree trunks.