Todorokite of chemical composition (Mg(0.77)Na(0.03))(Mg(0.18)Mn(2+)(0.60)Mn(4+)(5.22)22) O(12).3.07 H(2)O was synthesized by a two-step procedure. First, sodium birnessite was synthesized and magnesium was exchanged for sodium to form magnesium birnessite, which was autoclaved under a saturated steam pressure at 155 degrees C for 8 hours to form well-crystallized todorokite. Synthesized todorokite particles consisted of fibers extending from a central plate. The plate itself was made of twinned fibers forming a trilling pattern. The infrared spectra and x-ray diffraction patterns were similar to those of natural todorokite samples. Calcium birnessite and nickel birnessite, when autoclaved under conditions similar to those for magnesium birnessite, yielded a todorokite structure. However, the formation of todorokite from calcium and nickel birnessite was less extensive.