AbstractPesticides can improve crops' yield and quality, but unreasonable applications of pesticides lead to waste of pesticides which are further accumulated in the environment and threaten human health. Developing the release of controlled drugs can improve the utilization rate of pesticides. Among these methods, light‐controlled release is a new technology of controlled release, which can realize spatiotemporal delivery of drugs by light. Four compounds, named Imidacloprid‐Thioacetal o‐nitrobenzyl‐Phenamacril (IMI‐TNB‐PHE), Imidacloprid‐Thioacetal o‐nitrobenzyl‐ Imidacloprid (IMI‐TNB‐IMI), Phenamacril‐Thioacetal o‐nitrobenzyl‐Phenamacril (PHE‐TNB‐PHE), and Imidacloprid‐Thioacetal o‐nitrobenzyl‐Imidacloprid Synergist (IMI‐TNB‐IMISYN), were designed and synthesized by connecting thioacetal o‐nitrobenzyl (TNB) with pesticides TNB displaying simple and efficient optical properties in this work. Dual photo‐controlled release of pesticides including two molecules of IMI or PHE, both IMI and PHE, as well as IMI and IMISYN were, respectively, studied in this paper. Insecticidal/fungicidal activities of the photosensitive pesticides showed 2–4 times increments if they were exposed to light. In addition, a synergistic effect was observed after the light‐controlled release of IMI‐TNB‐IMISYN, which was consistent with the effect of IMISYN. The results demonstrated whether dual photo‐controlled release of the same or different pesticide molecules could be achieved with a TNB linker with spatiotemporal precision. We envisioned that TNB will be an innovative photosensitive protective group for light‐dependent application of agrochemicals in the future.