Abstract: Tip-enhanced Raman spectroscopy(TERS) plays an important role in the nanoscale characterization of structures and related physico-chemical properties due to its ultrahigh spatial resolution and ultrasensitive chemical recognition. In this review, we first present an overview on the recent advancements of high-resolution TERS and its applications in various fields, and then briefly review the possible underlying physical mechanisms of high-spatial resolution in TERS imaging. Finally, based on the ultrahigh-resolution TERS imaging, we introduce a new methodology called“Scanning Raman Picoscopy”(SRP) for the determination of molecular chemical structures. The review is concluded with a perspective on the future development of the SRP technique.