Bismuth layer-structured ferroelectrics (BLSFs) are one of the candidates for lead-free piezoelectrics for high temperature and high frequency applications. BLSFs have a layer structure with a general formula (Bi 2 O 2 )(A mÀ1 B m O 3m+1 ), where A denotes mono-, di-, or trivalent ions with a large ionic radius, and B denotes tetra-, penta-, or hexavalent ions with a small ionic radius, and m is an integer between 1 and 5. The crystal structure is composed of pseudo-perovskite blocks (A mÀ1 B m O 3m+1 )