The invention discloses a phenol recognition SERS probe, its preparation and application, and a SERS-based general ultrasensitive immune analysis method. First, DTDBA was used to reduce chloroauric acid to prepare a phenol-responsive SERS probe, then ELISA was combined with SERS, ALP was used to label biomolecules, and ALP was used to hydrolyze its substrate PPNa to produce phenol, and the SERS probe signal caused by phenol was thus Technologies to achieve sensitive detection of biomolecules. This technology can not only overcome the shortcomings of low sensitivity of conventional enzyme-linked immunoassays, but also solve the problems of SERS detection signal enhancement and poor reproducibility. The invention has remarkable universality, can be widely used in immunoassays using ALP as an enzyme marker to measure various biomolecules, and lays a solid foundation for the development of immune technology based on SERS detection, and can be used in the fields of biology, chemical detection, medical diagnosis, etc. All have great development space and broad application prospects.