This work aimed at investigating red wine olfactory–oral cross-modal interactions, and at testing their impact on the correlations between sensory and chemical variables. Seventy-four Italian red whole wines (WWs) from 10 varieties, and corresponding deodorized wines (DWs), were evaluated by sensory descriptive assessment. Total phenols, proanthocyanidins, ethanol, reducing sugars, pH, titratable and volatile acidity were determined. PCA results highlighted different sensory features of the 10 wine types. ANOVAs (p < 0.05) showed that olfactory cues might play modulation effects on the perception of in-mouth sensations with 7 (harsh, unripe, dynamic, complex, surface smoothness, sweet, and bitter) out of 10 oral descriptors significantly affected by odours. Three weak but significant positive correlations (Pearson, p < 0.0001) were statistically found and supported in a cognitive dimension: spicy and complex; dehydrated fruits and drying; vegetal and unripe. In the absence of volatiles, correlation coefficients between sensory and chemical parameters mostly increased. Proanthocyanidins correlated well with drying and dynamic astringency, showing highest coefficients (r > 0.7) in absence of olfactory–oral interactions. Unripe astringency did not correlate with polyphenols supporting the idea that this sub-quality is a multisensory feeling greatly impacted by odorants. Results support the significance of cross-modal interactions during red wine tasting, confirming previous findings and adding new insights on astringency sub-qualities and their predictive parameters.