The TE/TM polarization conversion characteristics of dielectric grating composed of left-handed materials for the case of plane wave oblique incidence are carefully investigated by a method which combines the multimode network theory with the rigorous mode matching method. It is indicated that complete polarization conversion between TE and TM modes can be realized using left-handed gratings. This can hardly achieve in the conventional right-handed gratings. Comparisons of polarization conversion properties between right-handed gratings and left-handed gratings are given with physical explanations. This unique merit of left-handed periodic structure is of important significance for accurate design of new millimeter wave TE/TM polarization converters.