The dissociative multiple photoionization of tetramethylgermane (Ge(CH3)4) in the valence, and in the Ge(3d,3p,3s) and C(1s) inner-shell regions has been studied by using time-of-flight mass spectrometry coupled to synchrotron radiation in the range 49.5–450eV. Total and individual photoion yields have been recorded as a function of the incident photon energy. Several discrete resonances over a structureless giant resonance are observed below the Ge(3p), Ge(3s) and C(1s) threshold regions. The structureless giant resonance corresponding to the Ge(3d) presumably arises from the continuum enhancement caused by the 3d→ϵf transition. Various monocations of H+, H2+, CHn+ (n=0–4), C2Hn+ (n=0–5), GeHn+, GeCHn+, GeC2Hn+, and GeC3Hn+ are detected in the whole energy range. Dissociation processes have also been investigated by photoelectron–photoion and photoion–photoion coincidence methods. The dominant dissociation channel is found to be CHn+–GeCHn+ in the whole energy examined. Specific energy dependence of dissociation processes is observed in the Ge(3p) and Ge(3s) regions. With the help of ab initio HF/6-311++G(2df,p) calculation, we roughly estimated the photoabsorption positions and symmetries for the discrete core hole states.