Insect antennal carboxylesterases (CXEs) play key roles in the process of ester odor degradation. In this study, 23 candidate CXEs were identified by transcriptome analysis of Grapholita molesta. The GmolCXE1 and GmolCXE5 were highly expressed in the antennae of adults and significantly up-regulated in the antennae of male moths after exposure with odors from female moths. GmolCXE7, 10, 13, 14 and 20-22 were abundantly expressed in the larval heads. The relative expression of GmolCXE13, 14 and 21 were significantly up-regulated after stimulation with odors from ripe fuji apples and crown pears. RNA interference assays demonstrated that the GmolCXE1, 5 and GmolCXE14, 21 may involve in regulating the adults’ mating and larval foraging respectively. Our study suggested that GmolCXE1 and GmolCXE5 could degrade the sex pheromone component (Z/E)-8-dodecenyl acetate to its product (Z/E)-8-dodecenol with evidence from EAG responses and GC-MS analysis. GmolCXE14, 21 could degrade odorant volatiles (Ethyl butanoate/ ethyl hexanoate) of ripe crown pears by GC-MS analysis. These GmolCXEs mediated foraging and mating would be potential and effective molecular targets to develop behavioral antagonists against larvae and adults of G. molesta.