Environmental change and biotic interactions both govern the evolution of the biosphere, but the relative importance of these drivers over geological time remains largely unknown. Previous work suggests that, unlike environmental parameters, diversity dynamics differ profoundly between the Palaeozoic and post-Palaeozoic eras. Here we use the fossil record to test the hypothesis that the influence of ocean chemistry and climate on the ecological success of marine calcifiers decreased throughout the Phanerozoic eon. Marine calcifiers build skeletons of calcite or aragonite, and the precipitation of these calcium carbonate polymorphs is governed by the magnesium-to-calcium ratio and temperature in abiotic systems. We developed an environmental forcing model based on secular changes of ocean chemistry and temperature and assessed how well the model predicts the proliferation of skeletal taxa with respect to calcium carbonate polymorphs. Abiotic forcing governs the ecological success of aragonitic calcifiers from the Ordovician to the Middle Jurassic, but not thereafter. This regime shift coincides with the proliferation of calcareous plankton in the mid-Mesozoic. The deposition of biomineralizing plankton on the ocean floor buffers CO2 excursions and stabilizes Earth’s biochemical cycle, and thus mitigates the evolutionary impact of environmental change on the marine biota.