Polarimetric passive millimeter-wave (PMMW) measurements can provide additional information about scenes. We report on the development of a 94GHz Multi-Polarization Scanning Imaging Radiometer (MPSIR) for outdoor imaging applications, and the polarization characteristic analysis of experimentally acquired images. The imager angular resolution is measured to be 0.37°, and the thermal sensitivity is about 0.46K. Multi-polarization measurements are realized by rotating the detector around the observation axis direction. Several outdoor complex scenes are selected to passive image, which include the outdoor parking lot and the dormitory buildings in the woods. Various polarization parameter images are generated to analyze the polarization characteristics. Based on the multi-polarization imaging, eight more polarization parameters are created and they are all have the special distribution properties. The experimental results indicate that the multi-polarization imaging and the modified polarization parameters have the great potential for three-dimensional reconstruction, edge detection and image segmentation.