A thermo-controlled pesticide release system composed of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) thin film grafted polydopamine (PDA) (PDMAEMA-g-PDA) microcapsules is reported. SiO₂ microparticles are used as a template to prepare PDA-coated SiO₂ microparticles. The thermally-responsive PDMAEMA thin films are grafted on PDA surfaces using a metal-free surface-initiated photopolymerization approach without adding any photo­initiator or photosensitizer under UV light irradiation. The subsequent acid etching yields PDMAEMA-g-PDA hollow microcapsules. PDMAEMA-g-PDA microcapsules exhibit well-controlled release of avermectin (Av). The results show that the loading ability of PDMAEMA-g-PDA microcapsules of Av is up to 52.7% (w/w). The release kinetics of Av demonstrate that Av@PDMAEMA-g-PDA microcapsules exhibit temperature-controlled release performance. This work is significant for controlled release systems. This simple design is expected to be used in various applications, such as in controlled drug release and agriculture-related fields.