Key odorants of red wine made from the hybrid grapes of Marselan (Vitis vinifera L.) were isolated by solid-phase extraction (SPE) and explored by gas chromatography-olfactometry (GC-O) analysis. Application of aroma extract dilution analysis (AEDA) revealed 43 odor-active compounds, and 31 odorants among them were detected with flavor dilution (FD) factors ranging from 9 to 2187. Comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry (GC × GC-TOF-MS) were exploited to quantitate the aroma-active compounds with FD ≥9. The identification indicated β-damascenone as having the highest FD factors, followed by eugenol, 2,3-butanedione, citronellol, 4-hydroxy-2,5-dimethyl-3(2H)-furanone, phenethyl acetate, guaiacol, and 2-methoxy-4-vinylphenol. A total of 21 compounds were found to have odor activity values (OAVs) >1.0. Aroma reconstitution validation experiments showed a good similarity of blackberry, green pepper, honey, raspberry, caramel, smoky, and cinnamon aroma attributes between the original Marselan wine and the reconstructed wine. In addition, omission tests were carried out to further determine the contribution of odorants to the overall aroma.