A series of saturated alkyl chain decorated triphenylamine amino derivatives (Ⅱb~d) were constructed through condensation reaction and selective reduction of polar double bond with metal boron hydride reactants using 4-{2-[N, N-bis(4-methylphenyl) aminophenyl]ethenyl}-benzaldehyde as starting materials. The synthetic route was optimized by controlling reaction time and charging sequence, gradient strengthening reductive ability of reductant. The results show that the ortho double bond of nitro group can be efficiently reducted with sodium borohydride at -5℃. However reduction of the ortho double bond of cyano group requires lithium boronhydride at 80℃ for as long as 10 h. Finally the triphenylamine amino derivates were linked to electron-deficient nitrogen heterocyclic unit (1,3,5-triazine) to form the corresponding covalently linked donor-acceptor (D-A) dyads. The products were characterized by 1HNMR, 13CNMR, high resolution mass spectrometry and infrared absorption spectroscopy. The results of UV-vis absorption, fluorescence emission and electrochemical measurements reveal the potential of these dyads to form long-lived charge-separated state for the application in photovoltaic devices.