It has been confirmed that octasulfonatocalix[8]arene (Calx-S8) and tris(2,2′-bipyridine)ruthenium (II) (Ru(bpy) 3 2+) can form a stable host–guest complex in aqueous solution. The binding constant for 1:1 [Calx-S8 8−·Ru(bpy) 3 2+] 6− complex formation was estimated to be (2.4±0.8)×10 4 dm 3 mol −1 by fluorescence titration, which indicates that the [Calx-S8 8−·Ru(bpy) 3 2+] 6− complex is the main species in 1:1 molar ratio aqueous solution of Calx-S8 and Ru(bpy) 3 2+. In situ UV–Vis spectroscopic measurements indicated that Ru(bpy) 3 2+ complexes can be readily deposited onto ITO electrode through electrochemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using [Calx-S8 8−·Ru(bpy) 3 2+] 6− host–guest complex as a dopant anion owing to the electrostatic interaction between the cationic conductive polymer and the anionic host–guest complex. The loading degree of the composite film with Ru(bpy) 3 2+ can be determined by Lambert-Beer law modified for the two-dimensional concentration. The obtained composite film showed good photoelectric conversion properties in response to visible light irradiation. This is a novel photocurrent generation system in which the photoexcited state energy is efficiently collected by the conductive polymeric layer.