Ocean acidification has occurred previously in Earth's history. It happened during the Capitanian mass extinction, at the end-Permian extinction, during the end-Triassic extinction, and during the Cretaceous–Palaeogene extinction event. 
Three of the big five mass extinction events in the geologic past were associated with a rapid increase in atmospheric carbon dioxide, probably due to volcanism and/or thermal dissociation of marine gas hydrates. Elevated CO levels impacted biodiversity. Decreased  saturation due to seawater uptake of volcanogenic CO has been suggested as a possible kill mechanism during the marine mass extinction at the end of the Triassic. The end-Triassic biotic crisis is still the most well-established example of a marine mass extinction due to ocean acidification, because (a) carbon isotope records suggest enhanced volcanic activity that decreased the carbonate sedimentation which reduced the carbonate compensation depth and the carbonate saturation state, and a marine extinction coincided precisely in the stratigraphic record, and (b) there was pronounced selectivity of the extinction against organisms with thick aragonitic skeletons, which is predicted from experimental studies. Ocean acidification has also been suggested as a one cause of the end-Permian mass extinction and the end-Cretaceous crisis. Overall, multiple climatic stressors, including ocean acidification, was likely the cause of geologic extinction events. 
The most notable example of ocean acidification is the Paleocene-Eocene Thermal Maximum (PETM), which occurred approximately 56 million years ago when massive amounts of carbon entered the ocean and atmosphere, and led to the dissolution of carbonate sediments across many ocean basins. Relatively new geochemical methods of testing for pH in the past indicate the pH dropped 0.3 units across the PETM. One study that solves the marine carbonate system for saturation state shows that it may not change much over the PETM, suggesting the rate of carbon release at our best geological analogy was much slower than human-induced carbon emissions. However, stronger proxy methods to test for saturation state are needed to assess how much this pH change may have affected calcifying organisms.