As a key member of benzoylurea insecticides, lufenuron exhibits a strong potential for bioaccumulation in ecosystems. Here, we report the synthesis of a molecularly imprinted polymer (MIP) and its application for selective extraction of lufenuron from agricultural runoff samples. The morphology and thermal stability of the prepared MIP was characterized by SEM and TGA, respectively. The experimental conditions for lufenuron detection were optimized through batch binding assay and response surface methodology (RSM). The MIP showcased a two-fold enhancement in binding capacity of lufenuron (74 mg g−1) relative to non-imprinted polymer (36 mg g−1), when measured through batch binding assay. Using a RSM based on central composite design, the qe value was predicted as 73.6 mg g−1 under optimal experimental conditions (e.g., pH 8). Furthermore, the percentage recovery of lufenuron was estimated as 98.8 ± 1.8% (n = 9). The adsorption kinetics of the MIP followed the pseudo-first-order model with χ2 value of 0.004 (correlation coefficient of 0.99). The limit of detection for lufenuron using MIP-based method was 3 × 10−6 µg mL−1. There was no significant decrease in the performance of MIP against lufenuron over five successive cycles.