Two new eight-layer hexagonal perovskites with the composition Ba8MNb6O24 (M = Fe and Cu) are synthesized by solid-state reaction at 1350-1400 degrees C. Their crystal structures have been investigated using X-ray and electron diffractions as well as high-resolution transmission electron microscopy. Although both compounds have similar M2+ size, Ba8MNb6O24 and Ba8MNb6O24 adopt shifted and twinned structures, respectively. Through comparison with the reported shifted Ba8MNb6O24 (M = Mn, Co, and Zn) and twinned Ba8MNb6O24 as well as inexistent Ba8Mg(Nb/Ta)(6)O-24, we elucidate that the twin-shift competition of Ba8MNb6O24 family could be related with multiple chemical factors including tolerance factors, B-cationic size difference, entropy variation with B-cation and vacancy disorder, Jahn-Teller distortion, and FSO B-B d orbit interactions.