Ground‐based and MErcury Surface, Space ENvironment, GEochemistry, and Ranging observations detected Ca0 and Ca+ in the exosphere of Mercury as well as unexpectedly high levels of sulfur on Mercury's surface. The mineral oldhamite ((Mg,Ca)S) could be a predominant component of the Mercury surface, particularly within the hollows identified within craters, and could therefore serve as a source of the observed exospheric calcium. Laboratory measurements on the photon‐stimulated desorption (PSD) of CaS powder (an analog for oldhamite) at a wavelength of λ = 355 nm have been conducted, utilizing resonance‐enhanced multiphoton ionization time‐of‐flight mass spectrometry to determine the yields and velocity distributions of Ca0. The desorbing Ca0 could be fit using two Maxwell‐Boltzmann components: a 600 (±30) K thermal component and a 1389 (±121) K nonthermal component, the latter accounting for ~25% of the observed signal. Cross sections for PSD using 3.4 eV photons were found to be 1.1 (±0.7) × 10−20 cm2 for Ca0 and 3.2 (±0.9) × 10−24 cm2 for Ca+. Adopting these cross sections, a Monte Carlo model of the release of Ca0 by PSD from the Tyagaraja crater finds the neutral microexosphere created from this process to be substantial even if only 1% CaS is assumed in the hollows. Diffuse reflectance UV‐visible measurements were made on the CaS powder to determine a bandgap, Eg, of 2.81 (±0.14) eV via the Tauc method.