Various nano-delivery systems have been designed to deliver synthetic/botanical pesticides for improved bioactivity. However, the enhanced toxicity of nanocarrier-loaded pesticides may injure the natural enemies, and their selective toxicity should be evaluated before the large-scale application. In this context, a star polymer (SPc)-based cyantraniliprole (CNAP) nano-delivery system was constructed, and its selective toxicity was evaluated using pest Frankliniella occidentalis (WFT) and predator Orius sauteri . The amide NH of CNAP could assemble with carbonyl groups or tertiary amines of SPc through hydrogen bonds to form CNAP/SPc complex spontaneously. The above self-assembly decreased the particle size of CNAP from 808 to 299 nm. With the help of SPc, the lethal concentration 50 (LC 50 ) values of CNAP decreased from 99 to 54 mg/L and 230 to 173 mg/L toward WFTs and O. sauteri due to the enhancement of broad-spectrum bioactivity. Interestingly, the toxicity selective ratio (TSR) of CNAP increased from 2.33 to 3.23 with the help of SPc, revealing the higher selectivity of SPc-loaded CNAP. To our knowledge, it was the first successful exploration of the selective toxicity of nanocarrier-loaded pesticides, and the higher selective toxicity of SPc-loaded CNAP was beneficial for alleviating the negative impacts on predators.