The biochemical composition of sweat is closely related to the human physiological state, which provides a favorable window for the monitoring of human health status, especially for the athlete. Herein, an ultra-simple strategy based on the surface-enhanced Raman scattering (SERS) technique for sweat analysis is established. Metal–phenolic network (MPN), an outstanding organic-inorganic hybrid material, is adopted as the reductant and platform for the in situ formation of Au-MPN, which displays excellent SERS activity with the limit of detection to 10⁻¹⁵ M for 4-mercaptobenzoic acid (4-MBA). As an ultrasensitive SERS sensor, Au-MPN is capable of discriminating the molecular fingerprints of sweat components acquired from a volunteer after exercise, such as urea, uric acid, lactic acid, and amino acid. For pH sensing, Au-MPN/4-MBA efficiently presents the pH values of the volunteer’s sweat, which can indicate the electrolyte metabolism during exercise. This MPN-based SERS sensing strategy unlocks a new route for the real-time physiological monitoring of human health.