Flowers have evolved remarkable diversity in flower color in response to pollinator-mediated selection. This diversity arises from specialized metabolic pathways that generate conspicuous pigments. Despite the clear link between floral reflectance spectra and floral pigment production, studies determining predictive relationships between pigmentation and petal reflectance are currently lacking. In this study, we analyze a dataset consisting of hundreds of natural Penstemon hybrids that are segregating flower color, including blue, purple, pink, and red. For each individual hybrid, we measured anthocyanin pigment production and petal reflectance. We found that floral pigment quantities are correlated with hue, chroma, and brightness as calculated from petal reflectance data: hue is related to the relative amounts of delphinidin vs. pelargonidin pigmentation, whereas brightness and chroma are correlated with the total anthocyanin pigmentation. We used a partial least squares regression approach to identify predictive relationships between pigment production and petal reflectance. We find that pigment quantity data provide robust predictions of petal reflectance, confirming a pervasive assumption that differences in pigmentation should predictably influence floral reflectance. Moreover, we find that reflectance data enables accurate inferences of pigment quantities, although the full reflectance spectra provide much more accurate inference of pigment quantities than spectral attributes (brightness, chroma, and hue). Our predictive framework provides readily interpretable model coefficients relating spectral attributes of petal reflectance to underlying pigment quantities. These relationships represent key links between genetic changes affecting anthocyanin production and ecological functions of petal coloration.