A pseudorotaxane monolayer consisting of a supramolecular complex generated between cyclo-bis(paraquat-p-phenylene), (1), and the 1,4-bis(mercapto ethyloxy ethyloxy ethyl)benzene monolayer, (2), that is stoppered by CdS nanoparticles (3-5 nm) is generated on Au electrodes. The surface coverage of the supramolecular complex units and the associated CdS particles corresponds to 2.4 +/- 0.2 x 10(-10) mole.cm(-2) and 3 x 10(12) particles.cm(-2), respectively. The photocurrent generated by the (1)/(2)-CdS pseudorotaxane architecture is 8-fold higher than in a CdS-nanoparticle monolayer system that lacks (1). The enhanced photocurrent in the pseudorotaxane assembly is attributed to vectorial electron transfer of photoexcited conduction-band electrons to the threaded electron acceptor (1), which leads to charge separation and to the retardation of the electron-hole recombination process.