Absolute pitch (AP) refers to the ability to effortlessly identify given pitches without any reference. Correlative evidence suggests that the left posterior dorsolateral prefrontal cortex (DLPFC) is responsible for the process underlying pitch labeling in AP. Here, we measured the sight-reading performance of right-handed AP possessors and matched controls under cathodal and sham transcranial direct current stimulation of the left DLPFC. The participants were instructed to report notations as accurately and as fast as possible by playing with their right hand on a piano. The notations were simultaneously presented with distracting auditory stimuli that either matched or mismatched them in different semitone degrees. Unlike the controls, AP possessors revealed an interference effect in that they responded slower in mismatching conditions than in the matching one. Under cathodal stimulation, this interference effect disappeared. These findings confirm that the pitch-labeling process underlying AP occurs automatically and is largely nonsuppressible when triggered by tone exposure. The improvement of the AP possessors' sight-reading performances in response to the suppression of the left DLPFC using cathodal stimulation confirms a causal relationship between this brain structure and pitch labeling.