The Diana Cave in SW Romania develops along a fault line and hosts a spring of hot (Tavg = 51 °C), sulfate-rich, sodium-calcium-chloride bearing water of near-neutral pH. Abundant steam and H2S rises from the thermal water to condensate on the walls and ceiling of the cave. The sulfuric acid produced by H2S oxidation/hydrolysis causes a strong acid-sulfate weathering of the cave bedrock generating a sulfate-dominated mineral assemblage that includes rapidcreekite, Ca2(SO4)(CO3)·4H2O closely associated with gypsum and halotrichite group minerals. Rapidcreekite forms bundles of colorless tabular orthorhombic crystals elongated along  and reaching up to 1.5 mm in length. For verifying the hydrogen bond scheme and obtaining crystal-chemical details of the carbonate group a single-crystal structure refinement of rapidcreekite was performed. Its unit-cell parameters are: a = 15.524(2), b = 19.218(3), c = 6.161(1) Å; V = 1838.1(5) Å3, Z = 8, space group Pcnb. Chemical composition (wt%): CaO 35.65, SO3 24.97, CO2 13.7, H2O 23.9, Na2O 0.291, MgO 0.173, Al2O3 0.07, total 98.75%. The empirical formula, based on 7 non-water O atoms pfu, is: Ca1.98Na0.029Mg0.013 Al0.004(S0.971 O4)(C0.97O3)·4.13H2O. The δ34S and δ18O values of rapidcreekite and other cave sulfates range from 18 to 19.5‰ CDT and from −9.7 to 7.8‰ SMOW, respectively, indicating that the source of sulfur is a marine evaporite and that during hydration of the minerals it has been an abundant 18O exchange with percolating water but almost no oxygen is derived from O2(aq). This is the first description of rapidcreekite from a cave environment and one of the very few natural occurrences worldwide. We also report on the mineral stability and solubility, parameters considered critical to understand the co-precipitation of carbonates and sulfates, a process that has wide applications in cement industry and scaling prevention.