As one class of the most important intermetallic compounds, the binary Laves-phase is well-known for its, abundant magnetic properties. Samarium iron alloy system SmFe2 is a prototypical Laves compound that shows strong negative magnetostriction, but relatively weak magnetocrystal line anisotropy. SmFe2 has been identified as a cubic Fd (3) over barm structure at room temperature; however, the cubic symmetry in principle, does not match the spontaneous magnetization along the [111]cubic direction. Here we studied the crystal structure of SmFe2 by high-resolution synchrotron X-ray powder diffraction, X-ray total scattering, and-Selected-area electron diffraction methods. SmFe2 is found to adopt a centrosymmetric trigonal R (3) over barm structure at room temperature, which transforms to an orthorhombic Imma structure at 200 K. This transition is in agreement with the changes of easy magnetization direction from [111]cubic to [110]cubic direction and is further evidenced by the inflection of thermal expansion behavior, the sharp decline of the magnetic susceptibility in the field-cooling zero field-cooling curve, and the anomaly in the specific heat capacity measurement. The revised structure and phase transformation of SmPe(2) could be useful to understand the magnetostriction and related physical properties of other RM2-type pseudocubic Laves-phase intermetallic compounds.