When the two-solution approach is used to make CaEGTA buffers, the most critical requirement is that the CaEGTA stock solution contain equimolar quantities of calcium and chelator. The impact on [Ca2+] of errors in the molar ratio is magnified at high buffer ratios, so stoichiometric imbalance is most readily detected there. In this paper we examine some of the properties of calcium buffer systems that illustrate these principles, and describe a simple and sensitive method for detecting and correcting stoichiometric imbalance in the CaEGTA stock solution. The method derives its high sensitivity from the fact that the CaEGTA stock solution itself represents a calcium buffer system with a very high buffer ratio.