The photoluminescent property of a bilayer of phthalocyanine and a perylene derivative, a part of an organic photovoltaic cell, was investigated. The monolayer of the perylene derivative exhibited photoluminescence at 824 nm with lifetimes of 1.6 ns and 0.10 ns. The steady state and time-resolved photoluminescence of the 100-nm perylene derivative layer were efficiently quenched with a 100-nm phthalocyanine coating. The high efficiency of the quenching was explained by the high mobility of the photogenerated carrier in the n-type semiconducting perylene derivative, and agreed with the insensitivity of the photovoltaic property of the bilayer to the thickness.