The brain takes the vital role in human physiological and psychological activities. The precise understanding of the structure of the brain can supply the material basis for the psychological behavior and cognitive ability of human beings. In this study, a fast molecular fingerprint analysis of mouse brain tissue was performed using surface-enhanced Raman scattering (SERS) spectroscopy. A nanohybrid consisting of flake-like black phosphorus (BP) and Au nanoparticles (BP-AuNSs) served as the novel SERS substrate for the spectral analysis of brain tissue. BP-AuNSs exhibited outstanding SERS activity compared to the traditional citrate-stabilized Au nanoparticles, which could be largely ascribed to the plentiful hot spots formed in the BP nanosheet. Rapid, full-scale and label-free SERS imaging of mouse brain tissue was then realized with a scanning speed of 56 ms per pixel. Fine textures and clear contour were observed in the SERS images of brain tissue, which could be well in accordance with the classical histological analysis; however, it could avoid the disadvantages in the processing procedure of tissue section. Additionally, the SERS spectra illustrated plentiful biochemical fingerprint of brain tissue, which indicated the molecular composition of various encephalic regions. The SERS difference spectrum of the left versus right hemisphere revealed the biochemical difference between the two hemispheres, which helped to uncover the psychological and cognitive models of the left and right hemispheres.