We propose a novel scheme of simultaneous polarization separation and switching, based on the orthogonallypolarized four-wave mixing (FWM) effect, for ultra-high-speed polarization multiplexing (Pol-MUX) fiber networks such as 100-Gbps and 400-Gbps backbone networks. We use theoretical and experimental analysis of the vector theory of FWM to successfully achieve polarization separation and all-optical switching by utilizing a 100-Gbps dual polarizationquadrature phase shift keying (DP-QPSK) signal and two orthogonally-polarized pumps. Both of the polarization-separated QPSK signals have clear constellation diagrams, with root mean square (RMS) error vector magnitudes (EVMs) of 14.32％ and 14.11％ respectively. The wavelengths of idlers can be created at 30 different wavelengths, which are consistent with Inteational Telecommunication Union-Telecommunication (ITU-T) wavelengths, by flexibly changing the wavelength of the pump light. Moreover, the idlers that have distinct wavelengths have power distributed in a range from -10 dBm to -15 dBm, which can support error-free transmission. The power penaltyis 5 dB lower than that of back-to-back (BTB) signal for both the X- and Y-polarization components measured at a bit error ratio (BER) of 3.8×10-3. Our experimental results indicate that this scheme has promising applications in future backbone networks.