Me3 TACN (1,4,7-trimethyl-1,4,7-triazacyclononane)-stabilized trimethylytterbium was obtained via a salt-metathesis protocol employing [(Me3 TACN)YbCl3 ] and methyllithium. Complex [(Me3 TACN)YbMe3 ] seems not to engage in redox chemistry with potassium graphite and is thermally quite stable in the solid state. Treatment of trivalent [(Me3 TACN)YbMe3 ] with 3 equiv. of AlMe3 afforded divalent tetramethylaluminate complex [(Me3 TACN)Yb(AlMe4 )2 ]. The reaction of [(Me3 TACN)YbMe3 ] with GaMe3 in THF gave trivalent ion pair [(Me3 TACN)YbMe2 (thf)][GaMe4 ], which is susceptible to reduction with KC8 . The thermally very labile divalent [(Me3 TACN)YbMe(μ-Me)]2 is the first discrete donor adduct of a divalent dimethyl rare-earth-metal complex.