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This paper presents a new unsupervised land cover/land use classification scheme using polarimetric synthetic aperture radar (PolSAR) imagery based on polarimetric scattering similarity. Compared with the H/alpha classification scheme based on a dominant “average” scattering mechanism, the proposed scheme has such advantages as the following: (1) The major scattering mechanism represents a target scattering in the low-entropy case; (2) it also represents both the major and minor scattering mechanisms in the medium-entropy case; and (3) all the scattering mechanisms in the high-entropy case can be represented. The major and minor scattering mechanisms have been identified automatically based on the relative magnitude of multiple-scattering similarities. The canonical scattering corresponding to maximum scattering similarity is regarded as the major scattering mechanism. The result obtained using the National Aeronautics and Space Administration/Jet Propulsion Laboratory's AIRSAR L-band PolSAR imagery reveals that the proposed scheme is more effective as compared to the existing models and promises to increase the accuracy of the classification and interpretation.