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Sensory interactions exist between 3-alkyl-2-methoxypyrazines and various volatiles in wines. In this study, the binary blending of Cabernet Franc wines containing high levels of MPs and three monovarietal red wines with two proportions was conducted after fermentation. Volatiles were detected by gas chromatography-mass spectrometry (GC-MS), and wines were evaluated by quantitative descriptive analysis at three-month intervals during six-month bottle aging. Results showed blending wines exhibited lower intensity of ‘green pepper’, especially CFC samples blended by Cabernet Sauvignon wines with an even higher concentration of 3-isobutyl-2-methoxypyrazine (IBMP). Based on Pearson correlation analysis, acetates could promote the expression of ‘tropical fruity’ and suppress ‘green pepper’ caused by IBMP. Positive correlation was observed among ‘green pepper’, ‘herbaceous’, and ‘berry’. The concentration balance between IBMP and other volatiles associated with ‘green pepper’ and fruity notes was further investigated through sensory experiments in aroma reconstitution. Higher pleasant fruity perception was obtained with the concentration proportion of 1-hexanol (1000 μg/L), isoamyl acetate (550 μg/L), ethyl hexanoate (400 μg/L), and ethyl octanoate (900 μg/L) as in CFC samples. Blending wines with proper concentration of those volatiles would be efficient to weaken ‘green pepper’ and highlight fruity notes, which provided scientific theory on sensory modification of IBMP through blending technique.