Methylviologen dications (MV2+) were immobilized between layers of manganese oxide during their electrochemicalassembly by an anodic route in a homogeneous aqueous Mn2+ solution. This approach yielded a well-ordered multilayerfilm on a platinum substrate as a result of dense packing of planar MV2+ molecules to stabilize the layered framework.A grazing angle in-plane X-ray diffraction study revealed that the manganese oxide sheets and the molecular planesof inserted MV2+ ions are oriented parallel to the electrode surface. Cyclic voltammetry of the product film indicatedan electron transfer from the underlying Pt substrate to inserted methylviologen ions through the manganese oxidesheets.