Abstract: The iron-rich calcareous soil (Typic Rhodustalf) from the Penghu island group represents a volcanic area. The black soils (Typic Haplustert, Vertic Endoaquoll, Typic Hapludolls) are typical of eastern Taiwan. Four A horizons and a pedon from the iron-rich calcareous soil and four pedons from the black soils were studied to analyze soil properties and clay compositions. The objective was to compare the properties of smectites developed from different parent materials. The materials were studied by using conventional X-ray diffraction (XRD) of K- and Mg-saturated clays and involved the alkylam-monium (C = 12) method and the Greene-Kelly test. The mean-layer charge of smectites (0.48–0.52 cmol(c)/O10(OH)2) in the iron-rich calcareous soil was found to be higher than the black soils (0.43–0.48 cmol(c)/O10(OH)2). A smectite of higher charge developed from the basalts. This smectite is enriched in Fe and Mg, and lacks Si, thereby forming beidellite and/or nontronite. In contrast, under high precipitation, elevated temperature, base saturation (e.g., Na, K, Ca, Mg), and about equal wet and dry cycles per year in the black soil environments, smectites developed from the complicated geologic site of eastern Taiwan. These smectites transformed to smectite-kaolinite mixed-layer clay and thus, resulted in lower-charge smectites. The K fixation capacity of the iron-rich calcareous soil was higher than the black soils.