The p-n heterojunction organic solar cell composed of n-type multilayer of two different perylene pigments and p-type metal-free phthalocyanine pigment was investigated. A downward potential step of the conduction band in the n-type multilayer enhanced the photocurrent quantum efficiency by a factor of about 3, owing to the suppression of the charge recombination of photogenerated carriers in the vicinity of the p-n junction. The multistep charge separation system consisting of energetically well-arranged organic thin layers was shown to offer an effective system to obtain highly efficient organic solar cells.