Based on the ambiguity function, a novel signal processing method for the polarization measurement radar is developed. One advantage of this method is that the two orthogonal polarized signals do not have to be perpendicular to each other, which is required by traditional methods. The error due to the correlation of the two transmitting signals in the traditional method, can be reduced by this new approach. A concept called ambiguity function matrix (AFM) is introduced based on this method. AFM is a promising tool for the signal selection and design in the polarization scattering matrix measurement. The waveforms of the polarimetric radar are categorized and analyzed based on AFM in this paper. The signal processing flow of this method is explained. And the polarization scattering matrix measurement performance is testified by simulation. Furthermore, this signal processing method can be used in the inter-pulse interval measurement technique as well as in the instantaneous measurement technique. Based on the ambiguity function, a novel signal processing method for the polarization measurement radar is developed. One advantage of this method is that the two polarization signals do not have to be perpendicular to each other. due to the correlation of the two transmitting signals in the traditional method, can be reduced by this new approach. A concept called ambiguity function matrix (AFM) is introduced based on this method. AFM is a promising tool for the signal selection and design in The polarizationforms of the polarimetric radar are categorized and analyzed based on AFM in this paper. And signal processing flow of this method is explained. And the polarization scattering matrix measurement performance is testified by simulation. method can be used in the inter-pulse interval measurement technique as well as in the instantaneous measurement technique.