Based on the polynomial interpolation, a new finite difference (FD) method in solving the full-vectorial guidedmodes for step-index optical waveguides is proposed. The discontinuities of the normal components of the electric field across abrupt dielectric interfaces are considered in the absence of the limitations of scalar and semivectorial approximation, and the present FD scheme can be applied to both uniform and non-uniform mesh grids. The modal propagation constants and field distributions for buried rectangular waveguides and optical rib waveguides are presented. The hybrid nature of the vectorial modes is demonstrated and the singular behaviours of the minor field components in the coers are observed. Moreover, solutions are in good agreement with those published early, which tests the validity of the present approach.