Based on MEAM (the modified embedded atom method) potential and an average atom model similar to B-W (Bragg-Williams) method, the distribution of Nb atoms in TiAl+Nb compounds with various composition was calculated. The calculation results showed that Nb atoms prefer to occupy the Ti sublattice of L10 structure for all compounds in question. With increasing atomic fraction of Nb and Al, Nb atoms exhibited a trend of ordered distribution on the Ti sublattice and result in a new L10 derivative superlattice structure.