Abstract: Microscopically ordered solid electrolyte architectures for solid-state and hybrid Li ion batteries are disclosed. The architecture comprises at least one porous scaffold comprising a lithium conducting ceramic that is porous enough to be infiltrated with cathode or anode active material in an amount sufficient to enable energy densities greater than 300 Wh/kg. Methods of making these microscopically ordered solid electrolyte architecture by fabricating at least one green ceramic scaffold and applying at least one heat treatment step are also disclosed.