It is of great significance to develop a simple and effective method for constructing large-scale high-quality surface-enhanced Raman scattering (SERS) substrate. Here Ag nanoparticle-assembled micro-bowl array was prepared by a close-packed polystyrene (PS) sphere monolayer templated electrodeposition approach. The fabricated Ag nanoparticle-assembled micro-bowl array shows high SERS sensitivity to rhodamine 6G (R6G) under an ultralow concentration of 1 fM, and exhibits excellent SERS spectral uniformity with a small relative standard deviation (RSD) of 7.6% and good reproducibility (a RSD ~8.2% for the average peak intensities from different batches of SERS substrates). The fabricated micro-bowl array SERS substrate was employed to detect pesticide residue (thiram and methyl parathion) on vegetables. The limit of detections (LODs) for the two pesticides are lower than the maximum residue limits (MRLs) set by European Union respectively, showing promising application in rapid inspection of food safety.