Novel thin films composed of a donor (D)/acceptor (A) charge-transfer chain compound were fabricated by a layer-by-layer technique using complexation of a paddlewheel-type diruthenium(II, II) complex with an N, N'-dicyanoquinonediimine derivative on an ITO substrate with a pyridine-substituted phosphonate anchor. The stepwise growth of an electron-transfer D+A(-)-chain thin film was confirmed.