This paper defines the wear process of rollers made of 20Cr4. Rollers with a diameter of 1000 mm were installed in a roller press used for the production of drop-shaped briquettes and the copper concentrate was briquetted for 1100 h. Three-dimensional (3D) geometry analysis, metallographic analysis, macroscopy, scanning electron microscopy, as well as hardness measurements were performed. It was observed that the working surface was non-uniformly worn. The smallest wear affects the molding cavities situated on the outermost edges of the ring. The wear increases as the center of the ring is approximated, and it reaches its maximum at the middle of the ring. The molding cavities also wear asymmetrically. For the shape considered in this study, the lower part of a cavity is subject to a higher wear rate. We found that the material of the working ring was carburized, but its hardness was significantly lower than required. The roller ring microstructure changes depended on the distance from the cavity’s face. An investigation of the wear mechanisms showed different types of abrasive wear, corrosive processes, and plastic deformation. The exact type and course of wear were described, depending on the location on the working surface.