New molecular dyads containing perylenediimide (PTCDI) as an electron acceptor and carbazolyl derivative as an electron donor have been successfully synthesized. Cyclic voltammetry and absorption spectroscopy show that both electroactive units preserve their intrinsic nature, whereas photophysical investigations display a efficient fluorescence quenching. The molecular dyads such as 4 and 5 exhibited unique electronic energy levels to facilitate the photoinduced electron transfer process.