For the ever-growing demand of advanced lithium-ion batteries, it is highly desirable to grow self-supported micro-/nanostructured arrays on metal substrates as electrodes directly. The in-situ growth of electrode materials on the conducting substrates greatly simplifies the electrode fabrication process without using any binders or conductive additives. Moreover, the well-ordered arrays closely connected to the current collectors can provide direct electron transport pathways and enhanced accommodation of strains arisen from lithium ion lithiation/delithiation. This article summarizes our recent work on design and construction of lithium-ion battery electrodes on metal substrates. An aqueous solution-based process and a microemulsion-mediated process have been respectively presented to control the kinetic and thermodynamic processes for the micro-/nanostructured array growth on metal substrates, with particular attention to CuO nanorod arrays and microcog arrays successfully prepared on Cu foil substrates. They can be directly used as binder-free electrodes to build advanced lithium-ion batteries with high energy, high safety and high stability. For the ever-growing demand of advanced lithium-ion batteries, it is highly desirable to grow self-supported micro- / nanostructured arrays on metal substrates as electrodes directly. The in-situ growth of electrode materials on the conducting substrates fabrication process without using any binders or conductive additives. Moreover, the well-ordered arrays closely connected to the current collectors can provide direct electron transport pathways and enhanced accommodation of ions arisen from lithium ion lithiation / delithiation. This article summarizes our recent work on design and construction of lithium-ion battery electrodes on metal substrates. An aqueous solution-based process and a microemulsion-mediated process have been respectively presented to control the kinetic and thermodynamic processes for the micro- / nanostructured array growth on metal substrates, with particular attention to CuO nanorod arrays and microcog arrays successfully prepared On Cu foil substrates. They can be directly used as binder-free electrodes to build advanced lithium-ion batteries with high energy, high safety and high stability.