Insertion of CO2 into the Li–N bond of two amidinolithium compounds [{LiN(2,6-Me2C6H3)C(H)N(2,6- Me2C6H3)}2(THF)3] and [{LiN(4-CH3C6H4)C(H)N(4-CH3C6H4)}2(THF)3] have been studied, and two lithium carbamate compounds [Li{O2C(N(2,6-Me2C6H3)C(H)N(2,6-Me2C6H3))}·THF]4 (1) and [Li{O2C(N(4-CH3C6H4)C(H)N(4-CH3C6H4))}·THF]6 (2) were obtained. The molecular structure of 1 shows a novel cage structure containing four eight-membered (LiOCOLiOCO) rings and two four-membered (LiOLiO) rings with the [Li4(CO2)4]4+ cluster in central. And an unusual and novel structure of 2 was obtained with a “wheel” cage structure including six six-membered (LiOLiOCO) rings surrounding the [Li6(CO2)6]6+ cluster. Both of 1 and 2 were fully characterized by elemental analysis, NMR spectroscopy, and X-ray structural determinations.