The evaluation of aroma-active profiles in dry-cured hams is crucial for determining quality, flavor, consumer acceptance, and economic value. This study characterized the volatile compounds in five varieties of dry-cured hams using gas chromatography-mass spectrometry-olfactometry (GC-MS-O) and an electronic nose (E-Nose). In total, 78 volatile compounds were identified across five varieties of dry-cured hams. A total of 29 compounds were recognized as aroma-active compounds. Odor description, intensity, and hedonic assessment were employed to evaluate these compounds. Black Hoof Cured Ham and Special-grade Xuan-Zi Ham contained higher levels of favorable compounds such as nonanal, 5-butyldihydro-2(3H)-furanone, and 2,6-dimethylpyrazine, contributing to sweet and popcorn-like notes. In contrast, Fei-Zhong-Wang Ham and Liang-Tou-Wu Ham exhibited higher proportions of off-odor compounds with lower hedonic scores. A principal component analysis clearly separated the five hams based on their aroma-active profiles, and a correlation analysis between E-Nose sensor responses and GC-MS-O data demonstrated a strong discriminatory ability for specific samples. These findings offer valuable insights into the chemical and sensory differentiation of dry-cured hams and provide a scientific basis for quality control, product development, and future improvements in E-Nose sensor design and intelligent aroma assessment.