The process mineralogy of potassium-rich shale from Chaoyang of Liaoning, China, was studied. Research results showed there are much less variety and smaller quantities in mineral compositions. Calculated mineral composition by means of chemical composition analysis combined with XRD, MLA, IR and TG-DSC analyses showed that main minerals with were Potassium-feldspar, muscovite, biotite and illite, and gangue minerals were quartz and small amounts of hematite. Potassium-rich minerals such as potassium-feldspar and muscovite contact smoothly with quartz respectively, and there was the direction arrangement among potassium-feldspar, quartz and muscovite in the shale. And quartz and hematite were main cement in the shale. The influences of the research results on the potassium extraction from potassium-rich shale were distinct.