Structural formulae and other crystallochemical parameters were used to study different species of dioctahedral micas in clay and coarse gravel fractions of horizons from a red soil (Ultic Haploxeralf) in southern Spain. Mineralogical analyses using X-ray powder diffraction, and measurements of the b 0 parameter revealed dioctahedral micas, illite and paragonite. Structural formulae established from electron microprobe analysis and energy dispersive X-ray analysis showed the illites to be K mica related in elemental composition and structure to muscovite and phengite. The paragonites were found to be closer to ideal mica. Structural formulae for Na-K dioctahedral micas were obtained with crystallochemical characteristics intermediate between those of Na micas and K micas. The possibility of these micas representing individual mineral phases or intergrowths of Na and K micas is discussed. In the soil profile, micas from the Bt horizon showed the largest crystallochemical changes induced by pedogenesis.