The tetragonal magnetostriction constant, (3/2)λ 100 , of Fe-Si single crystals was measured and was found to be structure dependent. Similar to that of Fe-Ge single crystals, (3/2)λ 100 is positive in the single phase A2 regime, becomes negative in the single phase D0 3 regime, and changes from positive to negative between the two regimes. Short-range order in the A2 regime decreases the magnetostriction prior to the onset of long range order. In the single phase regions of both A2 and D0 3 , thermal history does not show any obvious effect on the magnetostriction, contrary to that found for Fe-Ga alloys. However, in the regions of phase mixture involving A2, B2, and D0 3 phases, quenching pushes the change in magnetostriction from positive to negative to higher Si contents.