Single-molecule detection and imaging are of great value in chemical analysis,biomarker identification and other trace detection fields.However,the localization and visualization of single molecule are still quite a challenge.Here,we report a special-engineered nanostructure of Ag nanoparticles embedded in multi-layer black phosphorus nanosheets(Ag/BP-NS)synthesized by a unique photoreduction method as a surface-enhanced Raman scattering(SERS)sensor.Such a SERS substrate features the lowest detection limit of 10-20 mol L-1 for R6G,which is due to the three synergistic resonance enhancement of molecular resonance,photo-induced charge transfer resonance and electromagnetic resonance.We pro-pose a polarization-mapping strategy to realize the detection and visualiza-tion of single molecule.In addition,combined with machine learning,Ag/BP-NS substrates are capable of recognition of different tumor exosomes,which is meaningful for monitoring and early warning of the cancer.This work provides a reliable strategy for the detection of single molecule and a potential candidate for the practical bio-application of SERS technology.