This report describes the chemoselective coupling of polyfluoroarenes with aryl germanes in the presence of aromatic C-I, C-Br, C-CI, C-OTf, and C-SiMe3 groups, as well as demonstrates the further downstream diversification to give richly functionalized and highly fluorinated polyarenes. The strategy relies on an in situ Umpolung of the FnArH, followed by selective Au-(I)/Au-(III)-catalyzed coupling with electron-poor or -rich aryl germanes, even in the presence of challenging ortho-substituents, and widens the currently available coupling space in oxidative gold catalysis to previously inaccessible electron-poor/electron-poor biaryls.