As a part of the green process for manufacturing chromium compounds, two steps are involved in the synthesis of ultra-fine Cr 2 O 3 powders: the first is the hydrogen reduction of K 2 CrO 4 into intermediate trivalent (Cr 3+ ) or tetravalent (Cr 4+ ) chromium compounds; the second is the decomposing of the intermediate into Cr 2 O 3 by heat treating. The intermediate is well characterized by means of SEM, XRD, and XPS. The possible reaction mechanism of the process is analyzed.