Three dimensionally ordered macroporous membrane of a Li-ion conductive ceramic, Li–La–Ti–O (LLT), for all solid-state rechargeable lithium battery was prepared using colloidal templating process combined with sol–gel method. An opal structure consisting of mono-dispersed polystyrene beads (470nm in diameter) was used as a template. The preparation conditions of LLT membrane were optimized to obtain a relatively large size porous membrane. The LLT calcinated at 600°C was amorphous, and its Li-ion conductivity was 10−5 Scm−1 at room temperature. The composite electrodes of LLT–Li4Ti5O12 and LLT–LiMn2O4 were successfully prepared by sol–gel process.