WiFi has gradually developed into one of the main candidate technologies for indoor environment sensing. In this paper, we are interested in using COTS WiFi devices to identify material details, including location, material type, and shape, of stationary objects in the surrounding environment, which may open up new opportunities for many applications. Specifically, we present Wi-Painter, a model-driven system that can accurately detects smooth-surfaced material types and their edges using COTS WiFi devices without modification. Different from previous arts for material identification, Wi-Painter subdivides the target into individual 2D pixels, and simultaneously forms a 2D image based on identifying the material type of each pixel. The key idea of Wi-Painter is to exploit the complex permittivity of the object surface which can be estimated by the different reflectivity of signals with different polarization directions. In particular, we construct the multi-incident angle model to characterize the material, using only the power ratios of the vertically and horizontally polarized signals measured at several different incident angles, which avoids the use of inaccurate WiFi signal phases. We implement and evaluate Wi-Painter in the real world, showing an average classification accuracy of 93.4% for different material types including metal, wood, rubber and plastic of different sizes and thicknesses, and across different environments. In addition, Wi-Painter can accurately detect the material type and edge of the word "LOVE" spliced with different materials, with an average size of 60cm × 80cm, and material edges with different orientations.