The composition and evolutionary history of Mercury's crust are not well determined(1,2). The planet as a whole has been predicted(3) to have a refractory, anhydrous composition: rich in Ca, Al, Mg and Fe, but poor in Na, K, OH, and S. Its atmosphere is believed to be derived in large part from the surface materials. A combination of effects that include impact vaporization (from infalling material), volatile evaporation, photon-stimulated desorption and sputtering releases material from the surface to form the atmosphere. Sodium and potassium have already been observed in Mercury's atmosphere(4-6), with abundances that require a volatile-rich crust(7). The sodium probably results from photon-stimulated desorption(8,9), and has a temperature of 1,500 K (ref. 10). Here we report the discovery of calcium in the atmosphere near Mercury's poles. The column density is very low and the temperature is apparently very high (12,000 K). The localized distribution and high temperature, if confirmed, suggest that the atmospheric calcium may arise from surface sputtering by ions, which enter Mercury's amoral zone. The low abundance of atmospheric Ca may indicate that the regolith is rarefied in calcium.