A procedure was applied to recognise and classify particles of different composition (binary mixture of constituents) starting form the analysis of their morphological attributes. Development of non-destructive analytical techniques and the application of statistical methodologies are useful for process control starting from a small set of representative samples of the systems of particles to be processed. The results obtained demonstrated as a relationship exists between particle shape and mineral composition. The procedure was adopted for the classification of free and locked particles resulting from the comminution of a chromite ore.