A composite electrode between three-dimensionally ordered macroporous (3DOM) Li0.35La0.55TiO3 (LLT) and LiMn2O4 was fabricated by colloidal crystal templating method and sol–gel process. A close-packed PS beads with the opal structure was prepared by filtration of a suspension containing PS beads. Li–La–Ti–O sol was injected by vacuum impregnation process into the voids between PS beads, and then was heated to form 3DOM-LLT. Three-dimensionally ordered composite material consisting of LiMn2O4 and LLT was prepared by sol–gel process. The prepared composite was characterized with SEM and XRD. All solid-state Li-ion battery was fabricated with the LLT–LiMn2O4 composite electrode as a cathode, dry polymer electrolyte and Li metal anode. The prepared all solid-state cathode exhibited a volumetric discharge capacity of 220mAhcm−3.