Various tetrahedral heteroleptic Cu(I) complexes, as red organic light-emitting diodes (OLEDs), show a concern of maximizing the quantum yield (QY) in order to improve the optoelectronic performance. Herein, three experimental [Cu(N^N) (bis [2-(diphenylphosphino)phenyl]ether)]+ (named 1, 2 and 3) were selected as the jumping-off point, following two complexes (named 4 and 5) were successfully designed by introducing bulky electron-donating substituents into N^N ligands continuously. As expected, the QY of designed complexes 4 (0.26) and 5 (0.13) exhibit over twice higher than that of 3 (5.4 × 10−2). This can be attributed to the enhanced electron-donating property of N^N ligand, which accelerated the radiative transition rate (kr) through the apparently elevated energy level of the lowest triplet excited state (T1) and strengthened transition dipole moments, even though the spin-orbit coupling (SOC) effect is weakened. Simultaneously, the tetrahedral geometric distortion could be effectively restrained by the bulky N^N ligands, but the high vibrational freedom of the terminal substituents could also bring in some unfavorable intra-ligand deformation, resulting in an upward of the nonradiative transition rate (knr) at 5 (knr: 0.30 × 105 s−1 for 4; 0.95 × 105 s−1 for 5). Therefore, it's worth noting that the balance of excited state energy level, SOC effect as well as the reorganization energy ought to be elaborately regulated to achieve the optimal QY. This detailed investigation on the microscopic mechanism of these Cu(I) complexes can provide instructive inspiration for experimentalists.