Novel fluorinated subnaphthalocyanine derivatives were newly designed and synthesized as donor materials for low molecular organic photovoltaic cells using fullerene as an acceptor. They were designed to have the low-lying HOMO energy levels for improvement of open circuit voltage without any expense of short-circuit current density. The HOMO/LUMO energy levels of hexafluoro-, heptafluoro-, dodecafluoro-, tridecafluoro-and the parent subnaphthalocyanine estimated based on the photoelectron spectroscopy were-5.69/-3.93,-5.67/-3.90,-5.96/-4.19,-5.92/-4.11 and-5.30/-3.58 eV, respectively, showing that frontier orbital energy levels can be effectively tuned by fluorination.