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Stimulus-responsive materials containing selenide under oxidizing conditions have wide application prospects, especially in biomedicine. Due to the intricate preparation process, the scarcity of studies on the structure–activity relationship of regulatory factors in the oxidative stimulus response poses challenges to material design. Herein, based on selenol-ene chemistry, a diverse library of unsymmetric selenides is synthesized, enabling systematic investigation into the regulation of selenide oxidative elimination with variable substituent groups and positions. The α/β-positions of β-carbonyl unsymmetric selenides are efficiently modified with electron-donating or electron-withdrawing groups through a one-pot, two-step reaction involving ammonolysis of γ-selenobutyrolactone (SBL), followed by nucleophilic addition with unsaturated acrylate. In situ NMR tracking shows that the oxidative elimination of selenide had a distinct substituent effect. Both the electron and steric effects of the substituent influence the induction period of the selenide oxidative and elimination reactions. With the optimal substituent and position, the selenides would exhibit a timebomb-type response upon oxidation stimulus. Finally, a novel amphiphilic polymer comprising selenide-linked polyethylene glycol (PEG) and cholesterol moieties is synthesized as a representative ROS-sensitive material and exhibits a time-dependent reduction in micelle size. [ABSTRACT FROM AUTHOR]