This paper proposed a polishing path planning method of super accuracy mirror mold with free-form surface by curvature analysis. First, IGES files of free-form surfaces are read and the mold geometry is regenerated as B-spline surface by the Automatic Mold Polishing System (AMPS). By using the derivative properties of B-spline surface, normal vector and principal curvatures at any point of the surface are calculated. In addition, the effective contact width between polishing tool and mold surface based on the grain size and the principal radii of curvature is also determined. The minimum contact width in 3-D is mapped onto the (u, v) parameters of B-spline surface. Then a modified Peano fractal path with weaving function is calculated based on the effective contact width in the (u, v) coordinate. This Peano-weaving path was tested on an optical mold with free-form surface. The polishing result shows the method is very effective and achieves the level of mirror surface with roughness Ra 29nm.