Tuning the electron-donating ability (EDA) of the donor units of hole transporting materials (HTMs) is an efficient strategy to modulate the optoelectronic properties of HTMs. Based on this strategy, we first theoretically investigated the effects of the EDA of donor units on D-A-π-A-D architectural HTMs. The results show that the enhanced EDA of the donor unit leads to larger hole reorganization energy and poorer molecular stability of HTMs. In contrast, meta-substitution of side groups is an effective strategy to reduce the EDA of the donor unit. We found that the application of the meta-substitution strategy in the D-A-π-A-D system not only successfully improves the molecular stability, but also achieves higher hole mobility by promoting the electronic coupling between the molecular dimers and decreasing the hole reorganization energies simultaneously. Studies on interfacial properties indicate that intermolecular coupling also synergistically enhances the interfacial charge extraction performance and reduces carrier recombination. In conclusion, by utilizing the meta-substitution strategy to reduce the EDA of donor units on D-A-π-A-D architectural HTMs, we successfully designed four superior performance HTMs mD1, mD2, mD3, and mD4.