The tea geometrid, Ectropis grisescens Warren, is one of the most severe defoliator insect pests in tea plantations, China. The use of insecticides, etc., is forbidden on organic tea plantations. No female-produced sex pheromones of E. grisescens had been previously identified. In the present study, female gland extracts were analyzed by gas chromatography coupled with electroantennographic detection (GC-EAD) and two-dimensional gas chromatography (GC×GC) using a time-of-flight mass spectrometric detector (TOFMS). Two components, (Z,Z,Z)-3,6,9-octadecatriene (Z3Z6Z9-18:Hy) and (Z,Z)-3,9-6,7-epoxyoctadecadiene (Z3Z9-6,7-epo-18:Hy), were identified from pheromone gland extracts, and their electrophysiological and behavioral activity evaluated. Under laboratory conditions, Z3Z9-6,7-epo-18:Hy elicited a stronger electrophysiological response than Z3Z6Z9-18:Hy. In the field, traps baited with Z3Z9-6,7-epo-18:Hy alone showed better results than traps baited with Z3Z6Z9-18:Hy, and the binary mixture of Z3Z9-6,7-epo-18:Hy and Z3Z6Z9-18:Hy in a ratio of 4:1 (approximate ratio of females emitting pheromone) caught more males than the single components or any other blends. This study showed that Z3Z6Z9-18:Hy and Z3Z9-6,7-epo-18:Hy are the sex pheromone components of E. grisescens and that they prove useful in developing alternative management tools for the pest.