The epitaxial growth of ultrathin Fe film on Si(111) surface provides an excellent opportunity to investigate the contribution of magnetic anisotropy to magnetic behavior. Here, we present the anisotropic magnetoresistance (AMR) effect of Fe single crystal film on vicinal Si(111) substrate with atomically flat ultrathin p(2 × 2) iron silicide as buffer layer. Owing to the tiny misorientation from Fe(111) plane, the symmetry of magnetocrystalline anisotropy energy changes from the six-fold to a superposition of six-fold, four-fold and a weakly uniaxial contribution. Furthermore, the magnitudes of various magnetic anisotropy constants were derived from torque curves on the basis of AMR results. Our work suggests that AMR measurements can be employed to figure out precisely the contributions of various magnetic anisotropy constants.