The polarization properties of thermal millimeter-wave emission capture inherent information of objects, e.g., material composition, shape, and surface features. In this paper, a polarization-based material-classification technique using passive millimeter-wave polarimetric imagery is presented. Linear polarization ratio (LPR) is created to be a new feature discriminator that is sensitive to material type and to remove the reflected ambient radiation effect. The LPR characteristics of several common natural and artificial materials are investigated by theoretical and experimental analysis. Based on a priori information about LPR characteristics, the optimal range of incident angle and the classification criterion are discussed. Simulation and measurement results indicate that the presented classification technique is effective for distinguishing between metals and dielectrics. This technique suggests possible applications for outdoor metal target detection in open scenes.