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Two widespread lower Miocene rhyolite ash flow tuffs in the Kofa and Castle Dome mountains of southwestern Arizona are products of caldera‐forming eruptions. These closely erupted tuffs, the tuff of Yaqui Tanks and the tuff of Ten Ewe Mountain, are approximately 22 Ma in age and their eruptions culminate a 1‐ to 2‐m.y.‐long burst of calc‐alkaline volcanic activity centered on the northern Castle Dome Mountains. Exotic blocks of Proterozoic and Mesozoic crystalline rocks up to 20 m across are present in exposures of the tuff of Yaqui Tanks exposed in the central Castle Dome Mountains and the southern Kofa Mountains. A single, thick cooling unit of the tuff of Ten Ewe Mountain that includes thick lenses of mesobreccia marks the location of the younger caldera that extends from Palm Canyon in the western Kofa Mountains eastward more than 7 km along strike to the central part of the range. The tuffs show rapid thinning away from their inferred sources. They were probably associated with high‐volume (100 kms) eruptions. Large residual Bouguer gravity anomalies, one beneath each inferred caldera, are interpreted as batholithic rocks or low‐density caldera fill. Caldera‐related volcanism in the Kofa region occurred during a transition in extensional tectonic regimes: from a regime of east–west trending uplifts and basins to a regime manifest primarily by northwest striking normal faults. A narrow corridor of folding and strike‐slip faulting formed during volcanism in the southern Kofa Mountains. Upper Oligocene or lower Miocene coarse sedimentary rocks along the southern flank of the Chocolate Mountains anticlinorium in the southern Castie Dome Mountains mark the periphery of a basin similar to other early and middle Tertiary basins exposed in southern California. The volcanic section of the Kofa region was dissected by high‐angle normal faults related to northeast‐southwest oriented crustal extension typical of the southern Basin and Range province.