This study employed gas chromatography-mass spectrometry (GC-MS) in conjunction with gas chromatographyion mobility spectrometry (GC-IMS) to identify the characteristic volatile organic compounds (VOCs) in white peppers from global major production regions. Furthermore, the antioxidant activity of white pepper essential oil was evaluated, and the key volatile components were analyzed. The results revealed a total of 40 VOCs were identified, the predominant ones being terpenes and acids, which altogether accounted for over 80% of the identified compounds. Significant variations in the composition and concentrations of VOCs were observed among white pepper samples from different regions, which was the key factor contributing to the differences in their aroma profiles. Furthermore, the characteristic aroma of white peppers from different regions was primarily concentrated on fruity, floral, and other pleasant aromas, as well as undesirable odors such as fecal and sweaty notes. Additionally, a significant correlation was found between the antioxidant activity and volatile terpenes of white pepper essential oils. These findings provide a theoretical foundation for further exploration of the suitability of white peppers from different geographical origins for various processing applications.