Linear mixture models have been used to invert spectral reflectances of targets at the Earth's surface into proportions of plant and soil components. However, operational use of mixture models has been limited by a lack of biophysical interpretation of the results. The main objectives of this study were (1) to relate the deconvolved components of a mixture model with biophysical properties of vegetation and soil at the surface and (2) to apply the mixture model results to remotely sensed imagery. A radiative transfer model (SAIL: Scattering by Arbitrarily Inclined Leaves) was used to generate reflectance ‘mixtures’ from leaf and bare soil spectral measurements made at HAPEX-Sahel (Hydrological Atmospheric Pilot EXperiment) study sites. The SAIL model was used to create canopy reflectances and fractions of absorbed photosynthetically active readiation (fAPAR) for a range of mixed targets with varying leaf area index (LAI) and soils. A spectral mixture model was used to deconvolve the simulated reflectance data into component fractions, which were then calibrated to the SAIL-generated LAI, fAPAR and soil brightness. The calibrated relationships were validated with observational ground data (LAI, fAPAR and reflectance) measured at the HAPEX Sahel fallow bush/grassland, fallow grassland and millet sites. Both the vegetation and soil component fractions were found to be dependent upon soil background brightness, such that inclusion of the soil fraction information significantly improved the derivation of vegetation biophysical parameters. Soil brightness was also shown to be a useful parameter to infer soil properties. The deconvolution methodology was then applied to a nadir image of a HAPEX-Sahel site measured by the Advanced Solid State Array Spectroradiometer (ASA). Site LAI and fAPAR were successfully estimated by combining the fractional estimates of vegetation and soils, obtained through deconvolution of the ASAS image, with the calibrated relationships between vegetation fraction, LAI and fAPAR, obtained from the SAIL data.