We show that a belt of clockwise vertical-axis block rotation associated with dextral-oblique rifting in the Basin and Range province in Mexico hosted the localization of plate-boundary strain that led to formation of the Gulf of California ocean basin. Paleomagnetism of Miocene ignimbrites distributed widely across the rift reveals the magnitude, distribution, and timing of rotation. Using new high-precision paleomagnetic vectors (α95 ≈ 1°) from tectonically stable exposures of these ignimbrites in Baja California, we determine clockwise rotations up to 76° for intrarift sites. Low reference-site error permits isolation of intrarift block rotation during proto-Gulf time, prior to rift localization ca. 6 Ma. We estimate that 48% (locally 0%–75%) of the net rotation occurred between 12.5 Ma and 6.4 Ma. Sites of large (>20°) block rotation define an ∼100-km-wide belt, associated with strike-slip faulting, herein named the Gulf of California shear zone, which was embedded within the wide rift Basin and Range province and kinematically linked to the San Andreas fault. After a protracted history of diffuse extension and transtension, rift localization was accomplished by focusing of Pacific–North America dextral shear into the Gulf of California, which increased strain rates and connected nascent pull-apart basins along the western margin of the province. Oblique rifting thus helped to localize and increase the rate of continental break up and strongly controlled the three-dimensional architecture of the resultant passive margins.