The potassium pools of five major physiographic units of the Urmia region situated in western Azerbaijan province, north-west Iran, were studied to determine the distribution of K forms as functions of clay mineralogy and physiographic units. Soil samples from horizons of ten pedons were selected and analysed for physiochemical properties, clay mineralogy and forms of K. X-ray diffraction patterns revealed that the soils were similar in clay-mineral compositions, consisting of illite, smectite, chlorite, and kaolinite, for the different physiographic units, but vary in the relative amounts of these minerals. The illite content was highest in piedmont plain (P.P) followed by plateau (Pl), river alluvial plain (R.A.P), colluvial alluvial plain (C.A.R) and lowland (L.L) units. Smectite content was highest in Pl followed by P.P, L.L, R.A.P and C.A.P units. Several processes, such as the diversity of weathering rate, biocyclying processes of K accumulation, geomorphologic conditions and soil formation processes, caused significant differences in most K forms in the soils. A wide variation in total K (HF-extractable K) (0.54–1.1%), non-exchangeable K (280–450 mg kg–1) and exchangeable K (217–330 mg kg–1) occurred among the physiographic units, corresponding to variations in their mineralogical compositions, mainly the abundance of illite. Significant differences (P ≤ 0.05) were found for K, HNO3-extractable K and non-exchangeable K between the soils with large illite contents (30–50%) and with small illite contents (10–30%). A significant positive relationship existed between mineral K and illite content (r2 = 0.85, P ≤ 0.001) and non-exchangeable K and illite content (r2 = 0.84, P ≤ 0.001). The results indicated that these pools of K are mainly released from the frayed edges and wedge zones of illite.