The synthesis of metal chalcogenide aerogels Co0.5M0.33MoS4 (M= Sb or Y) by the sol-gel method is reported. In this system, the building blocks [MoS4]2− chelated with Co2+ and (Sb3+) or (Y3+) salts in nonaqueous solvents forming amorphous networks with a gel property. The chalcogels obtained after supercritical drying have BET surface areas of 176 m2 g−1 (Co0.5Sb0.33MoS4) and 145 m2 g−1 (Co0.5Y0.33MoS4). Electron microscopy and physisorption studies reveal that the new materials are porous with wide pore size distribution and average pore width of 16 nm. These chalcogels show higher adsorption capacity of toluene vapor (Co0.5Sb0.33MoS4: 387 mg g−1) and (Co0.5Y0.33MoS4: 304 mg g−1) over cyclohexane vapor and high selectivity of CO2 over CH4 or H2, Co0.5Sb0.33MoS4 (CO2/H2: 80 and CO2/CH4: 21), Co0.5Y0.33MoS4 (CO2/H2: 27 and CO2/CH4: 15). We also demonstrated that the impregnation of various metal species like Li+, Mg2+, and Ni2+ significantly enhanced the uptake capacity and selectivity of toluene and CO2 adsorptions in the chacogels.