The present disclosure provides a tip-enhanced Raman spectroscope system. The system includes a laser emitting unit, a laser excitation unit, a first dichroic beam splitter, a first Raman spectrometer, and a confocal detecting unit. The laser excitation unit includes a sample stage and a first scanning probe. The sample stage is configured to have a sample disposed thereon such that a first incident laser beam emitted from the laser emitting unit is transmitted to the sample to excite first scattered light. The first dichroic beam splitter is configured to split a first Raman scattered light from the first Rayleigh scattered light. The first Raman spectrometer is disposed on a first Raman optical path of the first Raman scattered light. The confocal detecting unit is disposed on a first Rayleigh optical path of the first Rayleigh scattered light to image the sample.