Surface-enhanced Raman scattering (SERS) greatly expands the applications of Raman spectroscopy and is a promising technique for food safety, environmental analysis, and public safety. Thin-film microextraction (TFME) provides an efficient sample preparation method for SERS to improve its selectivity and detection efficiency. This review comprehensively describes the development and applications of SERS and TFME, including the history, mechanisim, and active substrate of SERS and the theory, device, forms, and practical applications of TFME. The applications of TFME-SERS in food safety and environment monitoring are discussed, which could improve their advantages. TFME extracts and enriches the target analytes to eliminate the interfering substance, providing a facial way for SERS to analyze the target analytes in complex matrices. The development of TFME-SERS technology not only expands the application range of TFME, but greatly improves the anti-interference ability and detection sensitivity of SERS. Thus, the established methods are fast, convenient, and highly sensitive. This technology is potential to be applied in the on-site and real-time detection.