A sensitive and selective SERS sensor with easy and excellent recyclability is highly demanded because of its great potential application in complex detection environments. Here, using methylene blue (MB) as a model target, a semiconductor-based SERS substrate composed of a MoO₃ nanorod core and a uniform molecule-imprinting polymethacrylic acid shell (MIP) with a thickness of 4 nm was designed and fabricated (MoO₃@MIP) to achieve selective detection. The key to the successful coating of the ultrathin uniform MIP shell lies in the pretreatment of a MoO₃ core with nitric acid, providing sufficient surficial hydroxyls for the anchoring of a polymer precursor. The molecule-imprinted voids for MB were formed simply via light irradiation as a result of photocatalytic degradation by a MoO₃ semiconductor. This core–shell MIP composite shows a high SERS selectivity towards low-level MB in a mixed MB/CV solution. The enhanced factor (EF) is high, at 1.6 × 10⁴. More importantly, the selective detection allows the further photocatalytic recycling of MoO₃@MIP in an “aim-and-shoot” way, which well preserves the detection selectivity and sensitivity towards MB at least for 4 cycles. Based on decreased sensitivity with the increasing shell thickness (10–24 nm), a MIP-gating charge transfer mechanism is proposed to demonstrate the high EF instead of the molecule-enrichment effect. This “aim-and-shoot” strategy is expected to push forward the prosperous application of selective SERS for trace detection in versatile environments.