Disclosed is metal composite oxides having the new crystal structure. Also disclosed are ionic conductors including the metal composite oxides and electrochemical devices comprising the ionic conductors. The metal composite oxides have an ion channel formed for easy movement of ions due to crystallographic specificity resulting from the ordering of metal ion sites and metal ion defects within the unit cell. Therefore, the metal composite oxides according to the present invention are useful in an electrochemical device requiring an ionic conductor or ionic conductivity.