Lexical-chromatic synaesthesia is a condition in which letters and/or words elicit percepts of synaesthetic colours, termed photisms. Anecdotal data suggest that synaesthetes are particularly sensitive to inconsistencies between their synaesthetic percepts and the real world, e.g., it can be annoying and unpleasant for them to see a letter printed in a colour different than the respective photism colour. For R, a synaesthete subject who participated in the present study, the photisms possess specific emotional values (a red photism is pleasing and attractive, green is repulsive and unpleasant, etc.). In contrast to the anecdotal data, R does not always find the colour-photism incongruence to be disturbing. More importantly, he states that it is the emotional coherence between the stimulus and the corresponding photism that matters. In a series of experiments, we studied this new concept of emotional coherence on three levels—subjective (self-report), behavioural, and physiological, corroborating R's introspective statements. Besides the implications of the concept of coherence itself, the results presented here suggest that even highly subjective cognitive constructs can be approached and measured experimentally, uncovering the workings of the underlying psychophysiological mechanisms.