The Calán-ESO Proper-Motion Catalog (CE Catalog) contains 542 stars with proper motions >=0.2" yr-1, identified in 14 ESO areas in the southern hemisphere. Proper motions were measured from red IIIa-F plates taken 6-16 yr apart. Comparing the CE catalog with the Luyten and the Luyten half-second catalogs, we find that both suffer from incompleteness, which is particularly serious (<~40% complete) for mR>~13, where many of the astrophysically interesting object can be found. Proper motions, coordinates, estimated magnitudes, and finding charts for all objects in the catalog are provided. Based on plates obtained with the Schmidt Camera operated by ESO at La Silla, Chile. Project 64.H-0318.