Issues with the sluggish kinetics of oxygen reduction and oxygen evolution reduction hinder the advance of LiO2 batteries for next-generation energy storage. To alleviate these problems, Cu2O nanoparticles with different crystal planes have been synthesized via a simple solution reaction and characterized as a bi-functional catalyst for non-aqueous LiO2 battery. In this work, catalytic behaviour of Cu2O nanoparticles with different crystal planes are initially explored and it is found that the Cu2O nanoparticles exposing {111} crystal planes exhibit the most catalytic performance compared with other crystal planes, which is further confirmed by using first-principles computations. Inspired by selectively catalytic behaviour of crystal plane, porous Cu2O nanoframes exposed with eight {111} crystal planes and higher surface area derives from all-corner-truncated rhombic dodecahedron Cu2O nanoparticles are synthesized, which can act as highly activity three-dimensional cathode in a typical LiO2 battery after being directly combined with carbon nanotubes by electrostatic interaction. Thanks to the excellent catalytic activity of carbon nanotubes-Cu2O nanoframes and unique cathode structure, batteries with this cathode display an enhanced electrochemical performance including superior round-trip efficiency, excellent cycling performance and high specific capacity.