Optoelectric control of metal–organic frameworks would open up a new area of applications for hybrid materials. This article reports the calculated thermodynamic and electronic properties of a family of M3(C6X6) metal–organic frameworks (M = Mg, Ca, Zn, Cd, Hg, Ge, Sn, Pb; X = O, S, Se, Te). Herein, we present a systematic approach for studying families of hybrid compounds, and describe extended tunability of their electronic and enthalpic properties through compositional control. It was shown that the formation enthalpy is dictated by the stability of the ligand, and the band gap is tunable depending on both metal and chalcogenide selection. Five compounds were found to be candidate semiconductors as they combine thermodynamic stability with band gaps in the visible range of the electromagnetic spectrum.