A series of hexaaluminates, LaMnFexAl11-xO19-delta samples (x = 1, 2, 4, 6, 8) as new catalysts were prepared by carbonate precipitation and calcined at high temperature. Fe and Mn ions were used as active components to replace part of aluminum ions in the hexaaluminate lattices. The structures and properties of these samples were characterized by XRD, BET, and XPS. The series of hexaaluminates exhibited significant catalytic activity and stability at high temperature. The LaMnFe2Al9O19-delta retains a larger surface area and shows a good activity in methane combustion.