Herein, a novel technique that combined surface enhanced Raman scattering (SERS) with molecular imprinting was presented. In this study, SERS-active Ag particles with different surface morphologies were synthesized with the assistance of small acid molecules. Through the SERS investigation of different Ag morphologies, the Ag particles with a wool-ball surface morphology presented the perfect SERS capacity. Then, the Ag particles with a wool-ball surface morphology were used as the SERS substrate and combined via the technique of molecular imprinting to prepare SERS-MIPs for LC detection in a river. Under the optimal condition, a good linear relationship (R² = 0.98) was observed between the Raman signal (at 1595 cm⁻¹) and the concentration of the templates, and the limit of detection was 0.013 μmol L⁻¹. Moreover, the selective experiment proved that the specific selectivity of this material was due to the template. It has been confirmed that Ag-MIP is a kind of highly sensitive and selective sensor material for pyrethroid detection.