The standard of clinical care of most malignant solid cancers is surgery, followed by postsurgical adjuvant therapy, but microtumor lesions left behind after surgery and invisible distant metastases are the major reasons for treatment failure. Here, we report an integrated strategy combining surface-enhanced Raman spectroscopy (SERS) surgical navigation with postsurgical immunotherapy elicited by near-infrared II photothermal treatment and programmed death-1 antibody. The SERS surgical navigation is principally based on the multifunctional optical probes (namely, MATRA probes) integrating with T-weighted magnetic resonance (MR) imaging, photothermal effect and Raman spectroscopic detection. We demonstrate in a 4T1 breast tumor mouse model that the pre-surgical MR/SERS dual-modal imaging is capable of providing comprehensive tumor information, and intraoperative SERS detection allows accurately delineating the tumor margins and guiding the surgical resection in real time with the least residual microscopic foci. We verify that the postsurgical immunotherapy effectively eradicates those local microtumor lesions and invisible distant metastases, greatly inhibiting the postsurgical cancer recurrence and distant metastasis.