The effect of trivalent cations on the performance of Mg-M-CO(3) (M=Al, Fe, Ga, Mn) layered double hydroxides (LDHs) for high-temperature CO(2) capture is systematically investigated for the first time. We demonstrate that the M(3+) determines the structure evolution of LDH derivatives under thermal treatment, and finally influences the CO(2) capture capacity. Very different calcination temperatures are required for the different LDHs to obtain their maximum CO(2) capture capacities. To have a clear understanding of the reason behind these big differences the physicochemical properties, thermal stability, and memory effect of the LDHs were investigated. Both the thermal stability and the memory effect of LDHs are greatly influenced by the type of trivalent cation. The CO(2) capture capacities were also evaluated under various conditions. Another important finding of this work is that the quasi-amorphous phase obtained by thermal treatment at the lowest possible temperature gives the highest CO(2) capture capacity.