Agarwood is a precious aromatic plant which has good pharmacological effects such as antidepressant and sedation. It also has good ornamental and collection value. However, due to it is long and complex production process, the output of agarwood essential oils (AEOs) is scarce, so the price is expensive, the quality is uneven, and the adulteration events is endless. From the commercial and pharmaceutical point of view, the authenticity and quality of the commercial products labeled as AEOs is very important. This paper tested the applicability of Raman spectroscopy combined with chemometrics in classification and authenticity identification of AEOs. In this study, Raman spectroscopy and principal component analysis (PCA) combined with partial least square discriminant analysis (PLS-DA) were used to comprehensively evaluate AEOs from different geographical origins and/or extracted by different methods which showed different characteristic bands. The characteristic component of AEOs, chromone derivatives, and two commonly used adulterants were also detected. These characteristic bands provide spectrum information of AEO samples and reference materials, which can be used as Raman spectral markers for the qualitative identification of AEOs. This study can provide a novel, fast and convenient method for identification of AEOs.