Fluorene-cored dendrimers containing a triphenylamine chalcone unit at the periphery have been synthesized by divergent methodology using a click chemistry approach, and their photophysical and electrochemical properties have been investigated. All of the dendrimers exhibited quasireversible oxidation reduction signals in cyclic voltammetry. All of the dendrimers were used as additives in dye-sensitized solar cells (DSSCs), and the higher generation dendrimers exhibited better power conversion efficiency than the lower generation dendrimers in solar energy harvesting systems.