Threshold Photoelectron-Photoion Coincidence Spectroscopy (TPEPICO) has been used to study the ionic dissociation dynamics and energetics of Me6Ge2 (Me = CH3). Ions are energy-selected and the 0 K dissociation onsets for methyl and Me3Ge loss are obtained from the breakdown diagram and mass spectra distributions, both of them analyzed and modeled with statistical SSACM theory and quantum chemical (DFT, MP2) calculations. An updated value for the enthalpy of formation, ΔfHm0(g) of Me6Ge2, is used to derive ΔfHm0(Me3Ge,g) = 70.8 ± 8.9 kJ·mol−1. The bond dissociation enthalpies, BDE (Ge–X), of Me3Ge–X (X = Me, GeMe3, Cl and Br) were also derived in this study.