In order to enforce the electron withdrawn ability of traditional ethylene bond π bridge, focusing on the intramolecular reflux phenomenon in the electron transfer process of the classical D-A-π-A triphenylamine sensitized dye RL1, four different conjugated units, including benzene, thiophene, oxole, and pyridine, were added separately between the additional receptor Benzothiadiazole and π-bridge. Then the control regulation of the excitation property of dye RL1 was investigated based on First Principle Calculation. The results show that Benzothiadiazole could push and pull on the electron as the extra receptor. However, due to the strong electron-withdrawing ability of benzothiadiazole, the electron reflux will happen in the electron transfer process. Compared with dye RL1, the four conjugated units not only weaken the electron-withdrawing ability of benzothiadiazole, but also play a role as an electron donor, so the electron-withdrawing ability of cyanoacetic acid group can be significantly enhanced. So the research result can provide theoretical basis for further improving the photoelectric transformation efficiency of dyes in the design and preparation of dye molecules.