The aim of this work was to develop a diffuse reflectance methodology for quantifying minerals in powdered iron ores, which is a key quality control requirement for these materials. Selected samples ranging widely in their concentrations of hematite (as specularite and martite), goethite, magnetite, and quartz were collected in mines from the Iron Quadrangle, Minas Gerais State, and also in the Carajas region, Para State, Brazil. A chemometric analysis based on the concentrations of the different minerals as determined with a combination of conventional methods (chemical analysis, X-ray diffraction, Mossbauer spectroscopy, light-reflected microscopy, and magnetic susceptibility) and the principal components derived from the diffuse reflectance spectra in the visible range was performed. Principal component regression analysis provided successful calibration for the concentrations of goethite (r(2) = 0.94; standard error of validation (SEv) = 4.2%) and hematite (r(2) = 0.89; SEv = 7.4%), in addition to good estimates for quartz (r(2) = 0.83; SEv = 7.4%), specularite (r(2) = 0.80; SEv = 11.6%), and martite (r(2) = 0.78; SEv = 10.6%). Our results suggest that diffuse reflectance spectroscopy is a promising tool for the simultaneous determination of minerals in iron ores within a few minutes only. (C) 2009 Elsevier Ltd. All rights reserved.