Display omitted •PPy/Ca-alginate/Gel microsphere contained temperature-sensitive gelatin and sunlight-sensitive PPy.•PPy can convert the absorbed light into heat energy and cause the structural transition of gelatin.•Helix-coil structure transition of gelatin could promote the release of carbendazim.•PPy/Ca-alginate/Gel has great potential in agriculture for agrochemicals release. Responsive controlled-release systems can not only improve the efficiency of agrochemical utilization but also increase crop yield and reduce environmental pollution caused by excessive use of agrochemicals. In this paper, the helix-coil structural transition of gelatin was adopted to construct a novel stimuli-responsive controlled-release system called polypyrrole/Ca-alginate/gelatin (PPy/Ca-alginate/Gel). In PPy/Ca-alginate/Gel, Ca-alginate and gelatin form a semi-interpenetrating network in which uncross-linked gelatin can undergo a free helix-coil structural transition due to the photothermal effect of PPy. The structural transition of gelatin will lead to changes in the functional groups and microstructure of semi-interpenetrating hydrogels and furthermore achieve the release of template agrochemical molecules embedded in hydrogels. By using carbendazim as a template molecule, the photothermal conversion and controlled release of PPy/Ca-alginate/Gel were systematically studied. After 600 s of light irradiation, its temperature could be increased by 17 ℃. The release of carbendazim in microspheres reached 91.8 % after 8 h of light irradiation, while it was only 13.3 % in the dark. The results indicated that PPy/Ca-alginate/Gel have excellent controlled-release and sustained-release properties and broad application potential in agriculture.