The pile-up processing has a great impact on the flavor of white tea. To investigate the effects of the volatile accumulation of white tea with different piling thickness treatments, tea leaves from different thickness treatments were subjected to sensory quantitative description analysis and ATD-GC–MS detection in this study. As a result, 122 volatile components were identified from white tea with different treatments. A total of 8 key compounds, including isovaleraldehyde, isobutyraldehyde, 2-methyl-butanal, 1-octene-3-ol, linalool, pentanoic acid, hexanal and 1-hexanol were screened out using multivariate statistical analysis, which were characteristic components of grassy, floral-fruity, pekoe aroma and sweet flavors. The results of the selected key characteristic volatile compounds were consistent with the sensory quantitative description. The aroma of mid-pile dried tea (MD) was exhibited a harmonious and pleasant overall flavor. This study provides a novel insight into the accumulation of volatile during the withering step of white tea production.