Raman spectroscopy is a powerful technique in chemical information characterization. However, this spectral method is sub- ject to two obstacles in nano-material detection. One is diffraction limited spatial resolution, and the other is its inherent small Raman cross section and weak signaling. To resolve these problems, a new approach has been developed, denoted as tip-enhanced Raman spectroscopy (TERS). TERS is capable of high-resolution and high-sensitivity detection and demonstrat- ed to be a promising spectroscopic and micro-topographic method to characterize nano-materials and nanostructures. In this paper, the principle and experimental system of TERS are discussed. The latest application of TERS in molecule detection, bi- ological specimen identification, nanao-material characterization, and senti-conductor material determination with some spe- cific experimental examples are presented.