Oxidative addition reactions of dialkylchalcogenanes R₂E₂ and [Me₂Si(Nt-Bu)₂]Ge 1 yielded bis(alkylchalcogeno)germanes Me₂Si(Nt-Bu)₂Ge(ER)₂ (R = Et, E = S 2, Se 3; R = Me, E = Se 4) and digermanes [Me₂Si(Nt-Bu)₂Ge(EEt)]₂ (E = S 5, Se 6). The reaction of 1 with Et₂Te₂ proceeds with formation of Me₂Si(Nt-Bu)₂Ge(TeEt)₂7, which slowly converts into the Te-bridged complex [Me₂Si(Nt-Bu)₂GeTe]₂8. 1–6 and 8 were characterized by single crystal X-ray diffraction.