Nano-gold catalyzed transesterification of the (hetero)aryl ester with alkyl halides via C-O activation has been developed. In a series of supported AuNPs and PdNPs, the Au/γ-Al 2 O 3 catalyst with an AuNP mean diameter of 3.63 nm and 3 wt% Au loading exhibited the best catalytic performance. The catalyst can be reused and shows high activity after five cycles. The X-ray photoelectron spectroscopy (XPS) analysis of the catalyst before and after the reaction suggested that the reaction might be performed via a catalytic cycle that began with Au 0 .