Dicarboxamide is a class of special insecticide targeting at Ryanodine Receptor (RyR) with potent activity, new mode of action and eco-friendly characteristics in modern pest control. To explore new structures acting on RyR, a series of new dual chiral N-COCF3 sulfiliminyl derivatives were designed, synthesized, and characterized by melting point, 1 H NMR, high-resolution mass spectrometry (HRMS) and optical polarimeter. Their insecticidal activity against oriental armyworm (Pseudaletia separata Walker) were evaluated and the structure-activity relationship were summarized. The bioactivity revealed that some compounds showed favourable insecticidal activities against oriental armyworm. The sequence of these isomers' insecticidal activity was (Sc,Rs)≥(Sc,Ss). It was worth noting that compounds containing 2-CH3-4-Cl in the anilide moiety gave better activity than the compounds with 3-CF3. The study provided some important information for the further research of sulfiliminyl dicarboxamides.