The present investigation presents and correlates observed and reported characterization results of calcined, supported and unsupported chromias obtained via various precursor compounds. Studies performed employed a range of surface and bulk analytical techniques, in hopes of a proper assessment of the stability of surface chromate (Cr(VI)-O) species thus generated to thermal decomposition, hydrolysis and reduction. Impacts on the redox catalytic activity were probed towards the decomposition of H2O2 solutions and the CO oxidation in the gas phase. The results have revealed that chromate species established on bulk and dispersed alpha-Cr2O3 particles enjoy high stability against thermal and chemical treatments, and yet contribute to the formation of surface sites that are catalytically active in redox reactions. This should help lessening environmental reservations about the industrial application of calcined chromia catalysts.