In the present study, we acquired multi-angular polarized spectrum of three kinds of leaves with different surface structures, and calculated the multi-angular spectral degree of polarization DOP based on Stokes parameters to explore its variation tendency with wavelength and the relationship between the leaf polarized reflectance and its physiological parameters and the relative observational geometric condition. The results show that although the spectral degree of polarization of the 3 kinds of leaves has obvious differences in value because of the leaf surface structures, the general trend of the DOP curve keeps consistent, and this trend could be explained by analyzing the properties of both specular and diffuse components of the leaf reflectance. The peak value of the DOP appears in the specular direction of the principal plane, and grows with the increase in the incident zenith angle. The analysis of the data demonstrates that compared to the other two experimental bands, the near infrared band shows a better discrimination in showing the relationship between DOP and the observational geometric configuration for all the three kinds of leaves, but the value of the DOP is smaller. Considering the effect of variation in chlorophyll content, DOP of the red band has more stable value than the near infrared band, whereas the water content has barely influence in both of the bands.