The germanium monochalcogenide molecules Ge2S2, Ge2Se2, and Ge2Te2 were identified in a Knudsen cell mass spectrometric study of the vapors in equilibrium over solid GeS, GeSe, and GeTe. From a second and third law evaluation of the equilibrium data the following dimerization energies ΔH0,dimo were determined: 106.5 ± 2.1, 102.1 ± 4.6, 102 ± 8 kJ mol−1 for Ge2S2, Ge2Se2, Ge2Te2, respectively. These data and literature data allow to look into trends of the bonding energetics of group IVB‐VIB gaseous compounds.