We report the synthesis, characterization and possible applications of three new metal-chalcogenide aerogels KFe3Co3S 21, KFe3Y3S22 and KFe 3Eu3S22. Metal acetates react with the alkali metal polychalcogenides in formamide/water mixture to form extended polymeric frameworks that exhibit gelation phenomena. Amorphous aerogels obtained after supercritical CO2 drying have BET surface area from 461 to 573 m 2/g. Electron microscopy images and nitrogen adsorption measurements showed that pore sizes are found in micro (below 2 nm), meso (2-50 nm), and macro (above 50 nm) porous regions. These chalcogels possess optical bandgaps in the range of 1.55-2.70 eV. These aerogels have been studied for the adsorption of volatile hydrocarbons and gases. A much higher adsorption of toluene in comparison with cyclohexane and cyclopentane vapors have been observed. The adsorption capacities of the three volatile hydrocarbons are found in the following order: toluene > cyclohexane > cyclopentane. It has been observed that high selectivity in adsorption is feasible with high-surface-area metal chalcogenides. Similarly, almost an eight to ten times increase in adsorption selectivity towards CO2 over H2/CH4 was observed in the aerogels. Moreover, reversible ion-exchange properties for K+/Cs+ ions have also been demonstrated. © 2014 Elsevier Inc. All rights reserved.