First-principles calculations of the total energies of A2 iron and aluminum, B2 (FeAl), B32 (FeAl) and D03 (Fej Al and FeAb) compounds were performed in the frame of density functional theory (DFT) using the Full Potential - Linear Augmented Plane Wave method (FP-LAPW). These results have been used to obtain formation energies of the respective ground states. The calculated formation energies of the D03 (FejAl) and B2 (FeAl) compounds show excellent agreement with available calorimetric data on standard enthalpies of formation of Fe-Al alloys up to 50 at.% aluminum. As the Fe-Al system has a controversial magnetic behavior when described by ab-initio methods in the DFT, this agreement is remarkable. © 2003 Elsevier Science Ltd. All rights reserved.