Lithium is rare in the cosmos, but the formation of continental crust has concentrated lithium into economic deposits. The 124 recognized Li mineral species occur largely in four geologic environments: (1) lithium–cesium–tantalum (LCT) granitic pegmatites and associated metasomatic rocks; (2) highly peralkaline pegmatites; (3) metasomatic rocks not directly associated with pegmatites; (4) manganese deposits. The geologically oldest Li minerals are reported from LCT pegmatites and date to 3,000–3,100 Ma, a critical period in the evolution of the continental crust and the rate of its generation. This suggests a link between the earliest appearance of LCT-family pegmatites and the onset of plate tectonics, consistent with the correlation between the observed abundance of LCT-family pegmatites and supercontinent assembly.