Thin films of MoO(2) nanoparticles and graphene sheets are created by layer-by-layer (LBL) assembly as binder-free anodes for lithium-ion batteries. Both anionic polyoxometalate clusters and graphene oxide nanosheets with oxygen functional groups on both basal planes and edges are assembled into LBL films with the aid of a cationic polyelectrolyte. After a subsequent thermal treatment in an Ar-H(2) atmosphere, hybrid MoO(2)-graphene films with three-dimensionally interconnected nanopores are formed, which comprise ultrafine MoO(2) nanoparticles homogeneously embedded in the porous network of graphene nanosheets. When used as an anode for lithium-ion batteries, the MoO(2)-graphene thin-film electrode shows superior electrochemical performance with high specific capacity and excellent cyclability. A high specific capacity of 675.9 mA h g(-1) after 100 discharge-charge cycles is achieved, indicating a promising anode candidate for lithium-storage applications.