A technique is demonstrated for polarization demultiplexing of arbitrary complex-modulated signals. The technique is based entirely on the observation of samples in Stokes space, does not involve demodulation and is modulation format independent. The data in Stokes space is used to find the best fit plane and the normal to it which contains the origin. This normal identifies the two orthogonal polarization states of transmission and the desired polarization alignment transformation matrix. The technique is verified experimentally and is compared with the constant modulus algorithm.