Depending on the temperature, the twofold deprotonation of 1,1′‐methylenebis(3‐methylimidazole‐2‐thione) (1) and the subsequent reaction with 2 equiv. of trimethylsilyl chloride (TMSCl) gives two different bis‐TMS‐functionalized isomers, namely, 1,1′‐methylenebis(3‐methyl‐4‐trimethylsilylimidazole‐2‐thione) (2) and 1,1′‐methylenebis(3‐methyl‐5‐trimethylsilylimidazole‐2‐thione) (3). The cyclic dimethylsilyl‐bridged derivative 1,1′‐methylene‐5,5′‐dimethylsilylenebis(3‐methylimidazole‐2‐thione) (4) can also be obtained, corroborating the 5/5′ addition under certain conditions. All compounds have been examined by multinuclear 1D and 2D NMR experiments (1–4) together with single‐crystal X‐ray diffraction (3 and 4). Additionally, the dilithiated species 5 was synthesized by reacting 1 with 2 equiv. of nBuLi at ambient temperature in solution (THF). 1H and 7Li pulsed field‐gradient spin‐echo (PGSE) NMR, 7Li–1H heteronuclear Overhauser spectroscopy (HOESY), gradient heteronuclear multiple quantum correlation (gHMQC) and gradient heteronuclear multiple bond correlation (gHMBC) experiments showed that 5 exists as a monomeric contact ion pair (CIP) in THF solution. On the contrary, the X‐ray diffraction analysis of 5 revealed a polymeric chain, which can be described as [{5(thf)2}2]∞. Quantum chemical DFT and MP2 calculations were also conducted to determine the energies required for the deprotonation of 1. These results explain the regioselective deprotonation of 1 by CIP formation depending on the temperature and fully support the results of the synthetic and spectroscopic experiments.