Stimuli-responsive controlled release formulations offer a promising avenue for enhancing effective utilization and mitigating environmental risks of pesticides. Herein, pH and enzyme-responsive pesticide microcapsules (AVE@CPS-Fe-TA) were constructed by encapsulating carboxylated porous starch (CPS) loaded with avermectin (AVE) within tannic acid-iron complexes (Fe-TA) to improve the insecticidal efficacy and reduce toxicity to non-targets of AVE. The results showed that the loading content of AVE in the modified starch-based microcapsules could be precisely adjusted by the enzymatic hydrolysis time of starch. The prepared AVE@CPS-Fe-TA had pH and α-amylase dual responsive release properties and exhibited superior photostability, and its photolysis half-life was extended by 15.57-fold compared to AVE technical. Additionally, the leaf retention rate of AVE@CPS-Fe-TA after being rinsed by simulated rainwater was 6.08 times higher than that of commercial formulation AVE EC. In greenhouse insecticidal activity experiment, AVE@CPS-Fe-TA demonstrated a high control efficacy against Ostrinia furnacalis and had a prolonged effective duration. Moreover, AVE@CPS-Fe-TA significantly reduced the acute toxicity of AVE to zebrafish and promoted the growth of maize seedlings. Therefore, this work would provide eco-friendly stimuli-responsive microcapsules of pesticides for improving the efficiency of utilization and reducing environmental risks.