White electroluminescence (EL) spectra are carefully investigated in terms of the multilayer structures and a rule for designing the white luminescence is discussed. For a simple structure which consists of tris(8-hydroxyquinoline)-aluminum (Alq) and 1,2,3,4,5-pentaphenyl-1,3-cyclopendadiene (PPCP) emitting green and blue luminescence, respectively, as luminescent and electron transport layers, white luminescence appeared if the thickness of each layer was appropriately chosen. The luminescence efficiency was higher in PPCP, and therefore one of the structures effectively emitting white luminescence was designed as PPCP(10 nm)/Alq(40 nm). The 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) was then added to the PPCP/Alq structure intending to enhance red luminescence. We propose the structure where red luminescence is from the DCM as photoluminescence excited by the green and blue luminescence from Alq and PPCP, which was effective, compared to the PPCP/Alq/DCM stacking structure, in avoiding increase of the operating voltage. The importance of designing structures of organic white EL devices based on fundamental optical properties of the constituent layers and on luminescence dynamics is highlighted.