The possibility of estimating the concentration of individual photosynthetic pigments within vegetation from reflectance spectra offers great promise for the use of remote sensing to assess physiological status, species type and productivity. This study evaluates a number of spectral indices for estimating pigment concentrations at the leaf scale, using samples from deciduous trees at various stages of senescence. Two new indices (PSSR and PSND) are developed which have advantages over previous techniques. The optimal individual wavebands for pigment estimation are identified empirically as 680 nm for chlorophyll a, 635 nm for chlorophyll b and 470 nm for the carotenoids. These wavebands are justified theoretically and are shown to improve the performance of many of the spectral indices tested. Strong predictive models are demonstrated for chlorophyll a and b, but not for the carotenoids and the paper explores the reasons for this.