The formal insertions of carbon dioxide into a series of methylzinc dialkylamide complexes (MeZnNR2) initially form solvent-free, tetrameric zinc carbamato complexes [Me4Zn4(O2CNR2)(4)] (NR2 = N(i-Pr)(2) (1), N(i-Bu)(2) (2), and piperidinyl (3)). These compounds have been characterized by traditional techniques as well as by single-crystal X-ray diffraction analyses. The tetrameric backbones seen in the solid state for 1-3 were structurally similar to each other. Addition of excess pyridine (py) to 1-3 breaks apart the tetramers and converts them into solvated dimeric species [Me2Zn2(O2CNR2)(2)(py)(2)] (NR2 = N(i-Pr)(2) (4), N(i-Bu)(2) (5), and piperidinyl (6)). X-ray crystallographic analyses of 4 and 5 confirmed the dimeric structure in the solid state. This study significantly increases the number of well-characterized zinc carbamates prepared via CO2 insertion into zinc amides.