The chemical composition of dark chocolate has a significant impact on its complex flavor profile. This study aims to investigate the relationship between the volatile chemical composition and perceived flavor of 54 dark chocolate samples made from Trinitario cocoa beans from the Dominican Republic. The samples were evaluated by a trained panel and analyzed using gas chromatography-mass spectrometry (GC-MS) to identify and quantify the volatile compounds. Predictive models based on a partial least squares regression (PLS) allowed the identification of key compounds for predicting individual sensory attributes. The models were most successful in classifying samples based on the intensity of bitterness and astringency, even though these attributes are mostly linked to non-volatile compounds. Acetaldehyde, dimethyl sulfide, and 2,3-butanediol were found to be key predictors for various sensory attributes, while propylene glycol diacetate was identified as a possible marker for red fruit aroma. The study highlights the potential of using volatile compounds to accurately predict chocolate flavor potential.