To fabricate all-solid-state Li batteries using three-dimensionally ordered macroporous Li1.5Al0.5Ti1.5(PO4)3 (3DOM LATP) electrodes, the compatibilities of two anode materials (Li4Mn5O12 and Li4Ti5O12) with a LATP solid electrolyte were tested. Pure Li4Ti5O12 with high crystallinity was not obtained because of the formation of a TiO2 impurity phase. Li4Mn5O12 with high crystallinity was produced without an impurity phase, suggesting that Li4Mn5O12 is a better anode material for the LATP system. A Li4Mn5O12/3DOM LATP composite anode was fabricated by the colloidal crystal templating method and a sol–gel process. Reversible Li insertion into the fabricated Li4Mn5O12/3DOM LATP anode was observed, and its discharge capacity was measured to be 27mAhg−1. An all-solid-state battery composed of LiMn2O4/3DOM LATP cathode, Li4Mn5O12/3DOM LATP anode, and a polymer electrolyte was fabricated and shown to operate successfully. It had a potential plateau that corresponds to the potential difference expected from the intrinsic redox potentials of LiMn2O4 and Li4Mn5O12. The discharge capacity of the all-solid-state battery was 480μAhcm−2.