We investigated the Tuscan Italian colour inventory, with the aim of establishing the cognitive salience of the basic colour terms (BCTs) and most frequent non-BCTs. Native speakers from Tuscany (N = 89) completed a colour-term elicitation task lasting for 5 min. In total, 337 unique terms were elicited, with an average list length of 30.06. The frequency of each term, its mean list position and cognitive salience index (S) were calculated. The CTs with the highest S (ranked 1–13) included 10 counterparts of the Berlin and Kay BCTs listed in their 1969 seminal work and three basic ‘blue’ terms, blu, azzurro, celeste, estimated for Tuscan respondents by Del Viva et al. in 2022. S-index and Zipf-function (the terms’ “popularity”) indicated that fucsia (rank 14) is conceivably an emerging BCT in (Tuscan) Italian. Other cognitively salient non-BCTs are lilla, magenta, ocra and beige. The terms’ 3D semantic map (conceptual closeness), assessed using multidimensional scaling and cluster analysis, revealed that in the lists, closely associated CTs were arranged along three competing criteria: the term’s salience gradient; word length; and clustering of fully chromatic concepts with those defined primarily by lightness or desaturation. We also consider salient Italian non-BCTs as indicators of the ongoing process of lexical refinement in certain areas of the colour space. In conclusion, measures of elicitation productivity, as well as the augmented BCT inventory, including the Tuscan ‘triple blues’, and abundant hyponyms and derived forms all indicate (Tuscan) Italian speakers’ “cultural competence” in the colour domain and the need to communicate nuanced information about colour shades.