Leaf chlorophyll content is a key indicator of plant physiological status in viticulture; therefore, regular evaluation to obtain data for nutrient supply and canopy management is of vital importance. The measurement of pigmentation is most frequently carried out with hand-held instruments, destructive off-site spectrophotometry, or remote sensing. Moreover, smartphone-based applications also ensure a promising way to collect colorimetric information that could correlate with pigmentation. In this study, four grapevine genotypes were investigated using smartphone-based RGB (Red, Green, Blue) and CIE-L*a*b* colorimetry and a portable chlorophyll meter. The objective of this study was to evaluate the correlation between leaf chlorophyll concentration and RGB- or CIE-L*a*b*-based color indices. A further aim was to find an appropriate model for discriminating between the genotypes by leaf coloration. For these purposes, fully developed leaves of ‘Chardonnay’, ‘Sauvignon blanc’, and ‘Pinot noir’ clones 666 and 777 were investigated with the Color Grab smartphone application to obtain RGB and CIE-L*a*b* values. Using these color values, chroma, hue, and a further 31 color indices were calculated. Chlorophyll concentrations were determined using an Apogee MC100 device, and the values were correlated with color values and color indices. The results showed that the chlorophyll concentration and color indices significantly differed between the genotypes. According to the results, certain color indices show a different direction in their relationship with leaf pigmentation for different grapevine genotypes. The same index showed a positive correlation for the leaf chlorophyll concentration for one variety and a negative correlation for another, which raises the possibility that the relationship is genotype-specific and not uniform within species. In light of this result, further study of the species specificity of the commonly used vegetation indices is warranted. Support Vector Machine (SVM) analysis of the samples based on color properties showed a 71.63% classification accuracy, proving that coloration is an important ampelographic feature for the identification and assessment of true-to-typeness.