Abstract: To investigate the optimal processing parameters of cold plasma (CP) treatment for ‘Shine Muscat’ grapes and its effects on volatile compounds, ‘Shine Muscat’ grapes were treated with CP using processing time and voltage as experimental factors, while bacteriostatic rate and color difference (∆E) were used as evaluation indices. Response surface methodology was applied to optimize the CP conditions, and comprehensive volatile profiling was conducted using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS). The results showed that both processing time and voltage had significant effects on ∆E and bacteriostatic rate. The optimized parameters (252 s and 24 kV) yielded a bacteriostatic rate of 84.8% and a ∆E value of 1.94. A total of 59 volatile compounds were identified in grape berries, and the contents of alcohols, aldehydes, and terpenes increased significantly after CP treatment, resulting in a 43.99% increase in total volatile abundance. Orthogonal partial least-squares discriminant analysis effectively distinguished grape samples before and after CP treatment. Odor activity value analysis further revealed increases in key aroma compounds, including 1-hexanol, (E)-2-hexen-1-ol, phenethyl alcohol, linalool, and hexanal, which contributed to a more pronounced aromatic profile. Overall, CP treatment effectively preserved and enhanced the aroma quality of ‘Shine Muscat’ grapes. This study provides theoretical support and practical guidance for the application of CP technology in postharvest flavor modulation of table grapes.