Coccolithophores produce calcium carbonate platelets, the coccoliths, and play a significant role in the C and Ca cycles. Coccoliths are important components of marine biogenic carbonate sediments and their chemical analysis can provide tools for paleoceanographic investigation. In particular, the Mg/Ca ratio of coccoliths has been proposed as a paleotemperature proxy. The present study uses X-ray microanalysis to evaluate the Ca and Mg composition of heterococcoliths and holococcoliths of different coccolithophore species. Our measurements indicate that the Mg values in heterococcoliths do not exceed a low threshold and do not show any consistent relationship with the Ca content, while the Mg content of holococcoliths spans a wider range, can reach much higher values and shows a linear relationship with the Ca content. Several heterococcolithophore species tend to form separate clusters according to their Mg and Ca values. Within each cluster, there were no consistent differences in the Mg/Ca ratios of specimens sampled at different temperatures or seasons, suggesting that using the Mg/Ca ratio as a paleothermometer may be problematic. Our findings could have implications for the interpretation of the fossil record because Mg-rich calcite dissolves more easily.