A recent trend in homogeneous gold catalysis has been the development of oxidative transformations relying on Au(I)/Au(III) redox cycling. Typically, phosphine-supported Au(I) precatalysts are used in the presence of strong oxidants to presumably generate phosphine Au(III) intermediates. Herein, we disclose that such Au(III) complexes can undergo facile C-aryl-P reductive elimination to afford phosphonium salts, which have been spectroscopically and crystallographically characterized. Mechanistic studies indicate that this process occurs from cationic species at temperatures as low as -20 degrees C but can be accelerated in the presence of nucleophiles, such as acetonitrile and phosphines, via a five-coordinate intermediate. Importantly, this study highlights that irreversible C-aryl-P reductive elimination is a feasible decomposition or activation pathway for phosphine-supported Au(III) catalysts and should not be ignored in future reaction development.