A polarization-mode dispersion (PMD) measurement technique is described that allows the determination of second- and higher order PMD vectors in optical fibers. The algorithm, based on Muller matrices, requires the launch of only two polarizations per wavelength and uses large rotation angles as well as interleaving to attain low-noise high-resolution PMD data. It has been applied to fibers ranging from 2 to 40 ps in mean PMD.