The evolution of atomic ordering processes in Fe3Al has been modeled by the Monte Carlo (MC) simulation method combined with the electronic theory of alloys in pseudopotential approximation. The magnitude of atomic ordering energies of atomic pairs in the Fe3Al system has been calculated by means of electronic theory in pseudopotential approximation up to sixth coordination spheres and subsequently used as input data for MC simulation for more detailed analysis for the first time. The Bragg-Williams long-range order (LRO) and Cowley-Warren short-range order (SRO) parameters have been calculated from the equilibrium configurations attained at the end of MC simulation for each predefined temperature and Al concentration levels, which reveal the evolution of the system from DO3 --> B-2 --> disordered state as temperature increases. The variation of ordering parameters with temperature has identified the transition temperature from DO3 --> B2 type superlattice, and from B2 --> disordered (alpha) solid solution at about 540 degreesC and >900 degreesC, respectively, showing good qualitative agreement with experimental results. The results of the present study imply that combination of electronic theory of alloys in pseudopotential approximation with MC simulation can be successfully applied for qualitative or semiquantitative analysis of energetical and structural characteristics of atomic ordering processes in Fe3Al intermetallics.