A series of nickel foam (NF)-based composites of M x O y /RGO/Ni(OH)2 [M x O y = Co3O4, MnO2, and Ni(OH)2] with diverse multilayer nano-architectures were designed and grown in situ on NF through a one-pot hydrothermal process. Based on the redox reaction between the active NF substrate and graphene oxide (GO), along with electrostatic forces between the Mn+ ions and GO in the solution, strong interactions take place at the interfaces of M x O y /RGO, RGO/Ni(OH)2, and Ni(OH)2/Ni, and thus, there is good contact for electron transfer. These M x O y /RGO/Ni(OH)2 samples were directly used as conductive-agent- and binder-free anodes for lithium ion batteries (LIBs), and the Ni(OH)2/RGO/Ni(OH)2/NF composite electrode showed a high specific capacity, good rate capability, and excellent cycling stability, especially, it had a high reversible capacity of about 1330 mAh g−1 even after 200 cycles at 100 mA g−1. This general strategy presents a promising route for the design and synthesis of various multilayer nano-architectural transition metal oxides (hydroxide)/RGO composites on NF as energy storage materials.