The iron aluminides seem to be very perspective materials for high temperature structural application. They have many advantages, but unfortunately also some negative properties – e.g. sharp drop in strength above 600°C or limited ductility at room temperature. These disadvantages can be reduced by alloying of binary alloy by other elements.Present work deals with a study of coefficient of thermal expansion (CTE). It was investigated the influence of microstructure and heat-treatment on the values of CTE. Secondary, it was studied the possibilities, how to determine phase transition temperatures from CTE curves. Influence of type of iron aluminides lattice on CTE values was also examined as well as the influence of addition of alloying elements into binary iron aluminides.