This study investigates the aroma characterization of unique white tea varieties from the Lüchun county of Yunnan province, Mainland China. These include shaken, unshaken, steam-cooked, and compressed varieties. The aroma profile of white tea varieties was analyzed using two-dimensional gas chromatography–olfactometry–mass spectrometry (GC×GC-O-MS), electronic nose (e-nose), and descriptive sensory evaluation. A chemometric approach was used to compare sensory scores to instrumental data. A total of 154 volatile compounds were detected in 16 white tea varieties through GC×GC-O-MS. Among these, 133 compounds were successfully identified through the National Institute of Standards and Technology (NIST) library, and 21 were listed as unknown. The identified volatile classes include aldehydes, such as hexanal and heptanal, which contribute to the green aroma of white tea, and alcohols like 2-heptanol and 3-hexen-1-ol, which exhibit fresh and floral odor notes. The content and relative odor active values (r-OAVs) of the volatile compounds were calculated. The chemometric data revealed significant variations in volatile contents between shaken and unshaken white tea varieties. The orthogonal partial least squares discriminant analysis (OPLS-DA) model showed strong validity and stability. This study describes the impact of processing conditions on the flavor profile of white tea and provides a solid foundation for monitoring the aroma quality of different processed white tea varieties.