Artificial light‐harvesting systems have attracted great interest in biological photosynthesis and photo‐voltaic devices areas due to their unique structures, easy purification, low‐cost, and convenient processing abilities. Here, two dendritic molecules based on triphenylamine and naphthalimide have been designed and synthesized, their structures were confirmed by 1H NMR, ESI‐MS, and high resolution mass spectrometry. In these molecules, triphenylamine units perform as the electron donor moiety, and naphthalimide units perform as the electron acceptor. The obvious quenched fluorescence intensity and considerably shortened lifetime of the dendritic molecules combined with the molecular frontier orbital energy levels proved that the dendritic molecules not only are good candidates as hole‐transporting materials but also are two excellent photo‐induced electron transfer materials. Therefore, it is believed that these dendritic molecules have potential application value in photo‐voltaic devices.