The defects and subsurface damages induced by crystal growth and micro/nano-machining have a significant impact on the functional performance of machined products. Raman spectroscopy is an efficient, powerful, and non-destructive testing method to characterize these defects and subsurface damages. This paper aims to review the fundamentals and applications of Raman spectroscopy on the characterization of defects and subsurface damages in micro/nano-machining. Firstly, the principle and several critical parameters (such as penetration depth, laser spot size, and so on) involved in the Raman characterization are introduced. Then, the mechanism of Raman spectroscopy for detection of defects and subsurface damages is discussed. The Raman spectroscopy characterization of semiconductor materials’ stacking faults, phase transformation, and residual stress in micro/nano-machining is discussed in detail. Identification and characterization of phase transformation and stacking faults for Si and SiC is feasible using the information of new Raman bands. Based on the Raman band position shift and Raman intensity ratio, Raman spectroscopy can be used to quantitatively calculate the residual stress and the thickness of the subsurface damage layer of semiconductor materials. The Tip-Enhanced Raman Spectroscopy (TERS) technique is helpful to dramatically enhance the Raman scattering signal at weak damages and it is considered as a promising research field.