Leafy spurge can be detected during flowering with either aerial photography or hyperspectral remote sensing because of the distinctive yellow-green color of the flower bracts. The spectral characteristics of flower bracts and leaves were compared with pigment concentrations to determine the physiological basis of the remote sensing signature. Compared with leaves of leafy spurge, flower bracts had lower reflectance at blue wavelengths (400 to 500 nm), greater reflectance at green, yellow, and orange wavelengths (525 to 650 nm), and approximately equal reflectances at 680 nm (red) and at near-infrared wavelengths (725 to 850 nm). Pigments from leaves and flower bracts were extracted in dimethyl sulfoxide, and the pigment concentrations were determined spectrophotometrically. Carotenoid pigments were identified using high-performance liquid chromatography. Flower bracts had 84% less chlorophyll a, 82% less chlorophyll b, and 44% less total carotenoids than leaves, thus absorptance by the flower bracts should be less and the reflectance should be greater at blue and red wavelengths. The carotenoid to chlorophyll ratio of the flower bracts was approximately 1:1, explaining the hue of the flower bracts but not the value of reflectance. The primary carotenoids were lutein, β-carotene, and β-cryptoxanthin in a 3.7:1.5:1 ratio for flower bracts and in a 4.8:1.3:1 ratio for leaves, respectively. There was 10.2 μg g−1 fresh weight of colorless phytofluene present in the flower bracts and none in the leaves. The fluorescence spectrum indicated high blue, red, and far-red emission for leaves compared with flower bracts. Fluorescent emissions from leaves may contribute to the higher apparent leaf reflectance in the blue and red wavelength regions. The spectral characteristics of leafy spurge are important for constructing a well-documented spectral library that could be used with hyperspectral remote sensing.