Understanding the surface chemistry of solid catalysts is of great importance for the rational design of structures of advanced catalysts; however, long-term challenges remain due to the complex and non-uniform catalyst structures and the lack of suitable characterization techniques. Surface chemistry studies of single-crystal-based model catalysts with well-defined surface structures under ultra-high vacuum conditions have been developed as one approach, but the so-called materials gap and pressure gap are sometimes encountered when the acquired understanding is extended to the industrial reaction conditions. Recently emerging uniform catalytic nanocrystals with well-defined surface structures consist of a novel type of model catalysts, whose surface chemistry can be studied under the same conditions as the industrial reaction conditions; meanwhile, the surface chemistry of powder catalysts can be studied to some extent due to the development of advanced characterization techniques. Group IB metals (Cu, Ag, Au) and related oxides constitute a class of catalysts with unique catalytic properties and wide catalytic applications. We herein review the recent progress in the surface chemistry of Group IB metals and related oxides from single-crystal-based model catalysts to nanocrystal-based model catalysts and powder catalysts in an attempt to summarize the commonalities and to discuss the differences among the surface chemistry acquired from the catalysts with different levels of complexity. The surface chemistry of Group IB metals and related oxides is compared and correlated to their catalytic performance. A concept of model catalysts from single crystals to nanocrystals is prospected for the investigation of the surface chemistry of solid catalysts to approach industrial reaction conditions as closely as possible.