Mechanical peeling is more efficient and environmentally friendly compared to manual peeling. However, comparative studies on the quality of mechanically peeled pepper and manually peeled pepper are limited. This study utilized GC-MS to investigate the effects of immersion, steaming, and peeling machinery speed on the volatile composition of white pepper. A total of thirteen monoterpenes and seven sesquiterpenes were detected, with 3-carene, D-limonene, and sabinene being the most abundant monoterpenoids and β-caryophyllene, δ-elemene, and α-copaene being the most abundant sesquiterpenes. The total volatiles increased with longer steaming times and higher peeling machinery speeds. Compared to manual peeling or steaming followed by mechanical peeling, the volatile content of pepper was higher when using mechanical peeling alone. Additionally, relative odor activity values showed that 3-carene and D-limonene were the main contributors to flavor, with 3-carene, β-caryophyllene, and α-copaene being key volatiles responsible for flavor distinctions. This research aims to provide theoretical support for developing a superior and environmentally friendly mechanical method to replace manual labor.