Laser spectroscopic imaging techniques have received tremendous attention in the field of cancer diagnosis due to their high sensitivity, high temporal resolution, and short acquisition time. However, the limited tissue penetration of the laser is still a challenge for the in vivo diagnosis of deep-seated lesions. Nanomaterials have been universally integrated with spectroscopic imaging techniques for deeper cancer diagnosis in vivo. The components, morphology, and sizes of nanomaterials are delicately designed, which could realize cancer diagnosis in vivo or in situ. Considering the enhanced signal emitting from the nanomaterials, we emphasized their combination with spectroscopic imaging techniques for cancer diagnosis, like the surface-enhanced Raman scattering (SERS), photoacoustic, fluorescence, and laser-induced breakdown spectroscopy (LIBS). Applications of the above spectroscopic techniques offer new prospects for cancer diagnosis.