Successful isolation and unambiguous crystallographic assignment of a series of higher carbide cluster metallofullerenes present new insights into the molecular structures and cluster-cage interactions of endohedral metallofullerenes. These new species are identified as La2C2@C2(41)-C90, La2C2@D3(85)-C92, La2C2@C1(132)-C94, La2C2@C2(157)-C96, and La2C2@C1(175)-C98. This is the first report for these new cage structures except for D3(85)-C92. Our experimental and theoretical results demonstrate that La2C92-106 are more inclined to exist stably in the carbide form La2C2@C90-104 rather than as the dimetallofullerenes La2@C92-106, which are rationalized by considering a synergistic effect of inserting a C2 unit into the cage, which ensures strong metal-cage interactions by partially neutralizing the charges from the metal ions and by fulfilling the coordination requirement of the La3+ ions as much as possible.