Steeping process is an important factor for aroma release of tea, which has rarely been investigated for the aroma changes of raw Pu-erh tea (RAPT). In addition, the comprehensive aroma characteristics identification of RAPT infusion is necessary. In this study, GC−IMS coupled with principal component analysis (PCA) was used to clarify the difference of volatile profiles during the steeping process of RAPT. Furthermore, the volatiles contained in the RAPT infusion were extracted by three pretreatment methods (HS-SPME, SBSE, and SAFE) and identified using GC−O−MS. According to the odor activity value, 28 of 66 compounds were categorized as aroma-active compounds. Aroma recombination and omission experiments showed that "fatty", "green", "fruity", and "floral" are considered to be the main aroma attributes of RAPT infusion with a strong relationship with 1octen-3-one, 1-octen-3-ol, (E)-2-octenal, β-ionone, linalool, etc. This study will contribute a better understanding of the mechanism of the RAPT steeping process and volatile generation.