The effects of mechanical decortication parameters on the physicochemical properties of white pepper were analyzed. Specifically, the parameters investigated were whiteness, percentage of black berries, percentage of broken berries, piperine content, and pepper essential oil content. Five different maturation frequencies (10, 15, 20, 25, and 30 Hz) and four different decortication frequencies (25, 30, 35, and 40 Hz) were used for the analyses. To assess white pepper quality, fuzzy sensory evaluation and a numerical membership function were employed. The evaluation accounted for factors such as piperine content, composition and concentration of pepper essential oils, and sensory indexes including aroma, berry integrity, color, and degree of preference. The weight of each index was determined using the analytic hierarchy process (AHP). The results indicated that a maturation frequency of 20 Hz and a decortication frequency of 35 Hz yielded the optimal sensory scores (88.00 points). The numerical membership function calculations indicated that white pepper obtained with these parameters had the highest mean membership function values for positive attributes (2.71), suggesting they possessed the best quality of all experimental groups. In the analysis of white-pepper essential oils obtained with different decortication parameters, a total of 42 chemical compounds were identified. The compounds with the highest concentrations were 3-carene, β-caryophyllene, and limonene. These experimental findings provide valuable references for the sensory evaluation of white pepper and the optimization of white pepper production processes. Ultimately, they contribute to the enhancement of industrial white pepper production.