Highly ordered porous Cu2O film is electrodeposited on copper foil through a self-assembled polystyrene sphere template. Compared with the dense Cu2O film and the octahedral Cu2O powder, the ordered porous Cu2O film exhibits an improved electrochemical cycling stability. The capacity of the porous Cu2O film can maintain 336mAhg−1 and 213mAhg−1 after 50 cycles at the rate of 0.1C and 5C, respectively. The reversible capacity holds 63.4% as the discharge–charge rate even increases by 50 times. The enhanced high rate properties of the ordered porous film should be attributed to the sufficient contact surface of Cu2O/electrolyte and the short diffusion length of Li+. Moreover, the direct contact between Cu2O and current collector and the decreasing inactive interfaces of Cu2O/polymer binder are also suggested as being responsible for the enhanced high rate property.