An organic monolayer with diarylethene and viologen moieties as a photochromic and an electroactive group, respectively, was constructed on a hydrogen-terminated Si(111) surface by sequential surface reactions. Photoswitching behaviour of electron transfer from the Si electrode to viologen moiety, larger and smaller current after UV and visible irradiation, respectively, was observed. This photoswitching behaviour can be explained by a change in molecular conductivity of diarylethene moiety, which separates Si surface and viologen moiety, as a result of ring closing and opening induced by UV and visible irradiation, respectively. (C) 2009 Elsevier B.V. All rights reserved.