The correlation between the anthocyanin concentrations of seven Acer palmatum Thunb. cultivars and the chromaticity values a*, b*, a*/ b* ratio, h° and L* was investigated. According to the position of leaves on the branch terminal, middle and base sample leaves were analyzed and the positional effect on the level of the major anthocyanin was estimated. Leaf color was measured with a portable colorimeter and individual anthocyanins were detected with the use of HPLC–MS. Cyanidin-3-glucoside was present in all senescing leaves of Acer cultivars and its content decreased from terminal to base position. Cyanidin-3-rutinoside was identified in lower concentrations in the leaves of all cultivars. Multiple variable analysis was calculated for each of the tristimulus values and two major anthocyanins (cyanidin-3-glucoside, cyanidin-3-rutinoside) in senescing leaves of ornamental Acer cultivars. Correlations were detected between the major anthocyanin (cyanidin-3-glucoside) in analyzed Acer cultivars and all chromaticity parameters. The highest correlation coefficient (0.94) was observed between cyanidin-3-glucoside and a*/ b* ratio in cultivar ‘Bloodgood’ and lowest (0.54) between cyanidin-3-glucoside and a* in Acer palmatum Thunb. The correlation between cyanidin-3-rutinoside and chromaticity parameters was not detected in all Acer cultivars, additionally correlation coefficients and statistical significance were much lower. The expression of red color in both senescing leaves and in all-year-red cultivars can be tightly linked with the content level of cyanidin-3-glucoside; the second major anthocyanin does not contribute much to the red leaf color.