Amorphous ZnSnO3 double-shell and yolk-shell hollow microcubes were synthesized by calcination of their corresponding ZnSn(OH)6 precursors pre-prepared through a facile chemical solution method in argon. The as-prepared amorphous ZnSnO3 double-shell hollow microcubes have an average edge length of 1.6μm. When used as the anode materials, amorphous ZnSnO3 double-shell hollow microcubes (D-ZnSnO3) reveal better electrochemical properties than ZnSnO3 yolk-shell counterparts (Y-ZnSnO3). D-ZnSnO3 anodes can retain a high reversible capacity of 741mA h g−1 after 50 cycles with a coulombic efficiency of 99% at 100mA g−1. The amorphous feature and unique box-in-box hollow architecture of D-ZnSnO3 play a key role in their excellent electrochemical properties.