To identify the aroma compounds in a new lychee cultivar, Liniangxiang, a combination of headspace solid-phase microextraction (HS-SPEM) and gas chromatography-mass spectrometry (GC-MS) was used to analyze the aroma compounds in a new lychee cultivar ‘Liniangxiang’ and three common cultivars, namely ‘Guiwei’, ‘Nuomici’, and ‘Fengshanhongdenglong’. Discriminant models were established using orthogonal partial least squares discrimination analysis (OPLS-DA). Characteristic aroma compounds in the four lychee cultivars were identified based on their variable importance in projection (VIP), fold change (FC), and odor activity value (OAV). The results revealed 645 volatile compounds belonging to 16 chemical classes in the four cultivars, and terpenes were the dominant compounds. Based on the VIP and FC values, 391 volatile compounds showing significant differences among the four cultivars were identified. Subsequently, 41 characteristic aroma compounds were determined based on the criterion OAV>1. Clustering heatmap analysis indicated that these 41 compounds could be categorized into four distinct regions. Among them, region I contained 18 characteristic volatile aroma compounds such as 3-mercapto-3-methylbutyl formate ester, trans-2-nonanal, trans-2-cis-6-nonadienal, δ-cadinene, and p-cresol, which effectively distinguished ‘Liniangxiang’ from the other three cultivars. This distinction may contribute markedly to the unique flavor of ‘Liniangxiang’. This study provides valuable insights for the advancement and utilization of new lychee cultivars.