By using electric field induced optical second harmonic generation (EFISHG) and current voltage (I-V) measurements, we studied the electrical transport mechanism of organic double-layer diodes with a structure of Au/N, N'-di-[(1-naphthyl)-N, N'-diphenyl]-(1,1'-biphenyl)-4,4'-diamine (a-NPD)/poly(methyl methacrylate) (PMMA)/indium zinc oxide (IZO). Here the α-NPD is a carrier transport layer and the PMMA is an electrical insulating layer. The current level was very low, but the I-V characteristics showed a rectifying behavior. The EFISHG measurement selectively and directly probed the electric field across the α-NPD layer, and showed that the electric field across the a-NPD layer is completely relaxed owing to the charge accumulation at the a-NPD/PMMA interface in the region V > 0, whereas the carrier accumulation was not significant in the region V < 0. On the basis of these experimental results, we proposed a model of the rectification. Further, by coupling the I-V characteristics with the EFISHG measurement, the I-V characteristics of the diodes were well converted into the current-electric field (I-E) characteristics of the α-NPD layer and the PMMA layer. The I-E characteristics suggested the Schottky-type conduction governs the carrier transport. We conclude that the I-V measurement coupled with the EFISHG measurement is very useful to study carrier transport mechanism of the organic double-layer diodes.