Factors such as topography, mineralogy, physicochemical properties, and climate can affect the distribution of soil potassium (K) forms. However, often the special effects of physiographic units are neglected. Therefore, this study aimed to investigate the factors controlling the distribution of chemical fractions of K in different physiographic units of calcareous soils (piedmont plain, flood plain, alluvial plain, lowland, badland, and plateau) in southern Iran. The XRD analyzing patterns showed that the distribution of K forms is controlled by K-bearing minerals (i.e., illite) in finer particles of the soils. Physiographic units significantly affect the distribution of K forms due to different microclimates (such as soluble, exchangeable, and non-exchangeable). In addition, different correlations between the K forms and some physicochemical properties of the soils such as soil texture (i.e., silt (r = 0.511** to 0.527**) and sand (r = -0.357* to -0.389*)), electrical conductivity (EC) (r = 0.617** to 0.723**), sodium absorption ratio (SAR) (r = 0.478** to 0.577**), pH (r = 0.347* to 0.519**), and gypsum (r = 0.372* to 0.475**) were found in soils of the study area. It is recommended that cultivation sites are chosen with a deeper understanding of land conditions e.g., slope, elevation, microclimatic conditions, soil development, and clay mineralogy.