Sulfate and hydrated sulfate minerals are abundant and ubiquitous on the surface of the Earth and also on other planets and their satellites. The humidity-buffer technique has been applied to study the stability of some of these minerals at 0.1 MPa in terms of temperature-relative humidity space on the basis of hydration-dehydration reversal experiments. Updated phase relations in the binary system MgSO₄-H₂O are presented, as an example, to show how reliable thermodynamic data for these minerals could be obtained based on these experimental results and thermodynamic principles. This approach has been applied to sulfate and hydrated sulfate minerals of other metals, including Fe (both ferrous and ferric), Zn, Ni, Co, Cd, and Cu. Metal-sulfate salts play important roles in the cycling of metals and sulfate in terrestrial systems, and the number of phases extends well beyond the simple sulfate salts that have thus far been investigated experimentally. The oxidation of sulfide minerals, particularly pyrite, is a common process that initiates the formation of efflorescent metal-sulfate minerals. Also, the overall abundance of iron-bearing sulfate salts in nature reflects the fact that the weathering of pyrite or pyrrhotite is the ultimate source for many of these phases. Many aspects of their environmental significance are reviewed, particularly in acute effects to aquatic ecosystems related to the dissolution of sulfate salts during rain storms or snow-melt events. Hydrous Mg, Ca, and Fe sulfates were identified on Mars, with wide distribution and very large quantities at many locations, on the basis of spectroscopic observations from orbital remote sensing and surface explorations by rovers. However, many of these findings do not reveal the detailed information on the degree of hydration that is essential for rigorous interpretation of the hydrologic history of Mars. Laboratory experiments on stability fields, reactions pathways, and reaction rates of hydrous sulfates likely to be found on Mars enhance our understanding of the degrees of hydration of various sulfates that should currently exist on Mars at various seasons and locations and during various atmospheric pressure and obliquity periods. Two sets of systematic experiments were described; one on hydrous Mg sulfates and the other on hydrous Fe³⁺ sulfates. Also, their implications to Mars sulfates mineralogy were discussed.