Material classification using multiplexed illumination by broadband spectral light from multiple different incident angles, coupled with multi-spectral narrow band spectral measurement of light reflected from the illuminated object of unknown material, wherein selection of spectral bands for illumination or for narrow-band capture may comprise analysis of a database of labeled training material samples within a multi-class classification framework, captured using a relatively large number of spectral bands (such as 32 spectral bands), so as to select a subset of a relatively fewer number of spectral bands (such as 5 spectral bands), wherein the selected spectral bands in the subset retain a significant aptitude for distinguishing between different classifications of materials.