The two-coordinate carbene-metal-amide complexes have attracted a great deal of attention due to their remarkable thermally activated delayed fluorescence (TADF) properties, giving them promise in organic light-emitting diode application. To reveal the inherent mechanism, we take CAAC-Cu(I)-Cz and CAAC-Au(I)-Cz as examples to investigate the photophysical properties in solution and solid phases by combining quantum mechanics/molecular mechanics approaches for the electronic structure and the thermal vibration correlation function formalism for the excited-state decay rates. We found that both intersystem crossing (ISC) and its reverse (rISC) are enhanced by 2-4 orders of magnitude upon aggregation, leading to highly efficient TADF, because (i) the metal proportion in the frontier molecular orbitals increases, leading to an enhanced spin-orbit coupling strength between S1 and T1, and (ii) the reaction barriers for ISC and rISC are much lower in solution than in aggregate phases through a decrease in energy gap ΔEST and an increase in the relative reorganization energy through bending the angle ∠C2-Cu-N1 for T1. We propose a pump-probe time-resolved infrared spectroscopy study to verify the mechanism. These findings can clarify the ongoing dispute over the understanding of the high TADF quantum efficiency for two-coordinate metal complexes.