In article number 1500954 Sang‐Young Lee and co‐workers present the superlattice crystals‐mimic, flexible/functional ceramic membrane as a new ceramic‐driven material/architecture opportunity for next‐generation high‐performance battery separators. The structural uniqueness and Mn2 ‐chelating ability of the ceramic membrane (composed of close‐packed, thiol groups‐containing silica particles spatially besieged by the electrospun nanofiber skeleton) enable an unprecedented improvement in the membrane properties and cell performance far beyond those accessible with conventional polymeric separators.