In this work, a new surface plasmon resonance (SPR) sensor based on sulphur-doped titanium dioxide (S-TiO₂) nanostructures and molecularly imprinted polymer (MIP) was presented for thiram (THI) determination in milk samples. Firstly, the S-TiO₂ nanomaterial with a high product yield was prepared by using a facile sol-gel hydrolysis technique with a high product yield. After that, UV polymerization was carried out for the preparation of the THI-imprinted SPR chip based on S-TiO₂ using a mixture including ethylene glycol dimethacrylate (EGDMA) as the cross-linker, N,N′-azobisisobutyronitrile (AIBN) as the initiator, and methacryloylamidoglutamicacid (MAGA) as the monomer. The reliability of the sensor preparation procedure has been successfully proven by characterization studies of the prepared nanomaterials and SPR chip surfaces through spectroscopic, microscopic, and electrochemical methods. As a result, the prepared SPR sensor showed linearity in the range of 1.0 × 10⁻⁹–1.0 × 10⁻⁷ M with a detection limit (LOD) of 3.3 × 10⁻¹⁰ M in the real samples, and a sensor technique for THI determination with high sensitivity, repeatability, and selectivity can be included in the literature.