The title compound (4aR,7aS)-6-benzyl-1-((R)-2-(2-chlorophenyl)-4,5-dihydrothiazole-4-carbonyl)- hexahydro-5H-pyrrolo[3,4-b]pyridine-5,7(6H)-dione (C₂₄H₂₂ClN₃O₃S) was synthesized, and its chemical structure was confirmed by ¹H NMR, ¹³C NMR and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic system, space group C2/c with a = 28.929(6), b = 7.858(16), c = 22.936(5) Å, β = 125.20(3)°, V = 4221.4(15) ų, Z = 8, D_c = 1.473 g/cm³, μ(MoKa) = 0.314 mm^–1, the final R = 0.0629 and wR = 0.1708 for 2812 observed reflections with I > 2σ(I). The preliminary insecticidal activity indicated that the title compound exhibited good and promising insecticidal activities against Mythimna separata, Plutella xylostella and Culex pipiens pallens. Moreover, the calcium imaging experiment indicated that the title compound can activate intracellular calcium channels to release the stored calcium ion from endoplasmic reticulum (ER) to cytoplasm of Mythimna separata.