Citri reticulatae pericarpium (CRP), the dried pericarps of Citrus reticulata Blanco and its cultivars, has been widely used in drugs and foods in China for centuries. In this study, an accurate and feasible analytical method based on HS-SPME-GC-MS coupled with multivariate statistical analyses was developed to comprehensively compare volatile compounds of pericarps derived from Citrus reticulata “Chachi” (“Guangchenpi” in Chinese, GCP) and other cultivars of Citrus reticulata Blanco (“Chenpi” in Chinese, CP). Principal component analysis, hierarchical cluster analysis, and orthogonal partial least-squares-discrimination analysis were performed to extract meaningful attributes from volatile profiles based on GC-MS data. Results indicated that samples from GCP and CP could easily be differentiated, and seven potential chemical markers were screened for the quality control of CRP. This study illuminated the volatile profile in CRP, and provides a practical method for the authentication of CRP varieties.