The Fe-W system is systematically investigated through a combined use of first-principles calculation, cluster expansion, special quasirandom structures, and experiments. It is revealed that the ferromagnetic state of BCC Fe-W solid solution has lower heat of formation than its nonmagnetic state within the entire composition range, and intermetallic λ-Fe2W and μ-Fe7W6 phases are energetically favorable with negative heats of formation. Calculations also show that the Fe-W solid solution has much lower coefficient of thermal expansion than its mechanical mixture, and that the descending sequence of temperature-dependent elastic moduli of each Fe-W solid solution is E > G > B. Moreover, magnetic state should have an important effect on mechanical properties of Fe-W phases, and electronic structures can provide a deeper understanding of various properties of Fe-W. The derived results agree well with experimental observations, and can clarify two experimental controversies regarding structural stability and magnetic property of Fe-W phases in the literature.