Compound[Ag 44 (W 10 O 32 )(S t Bu) 24 (CF 3 COO) 8 ](CF 3 COO) 6 • 6H 2 O (1) was synthesized through a one-pot method. This is the first case of isolating a new silver thiolate cluster containing a [W 10 O 32 ] 6À template which transforms from WO 4 2À polyoxoanion through a self-assembly process. The anionic nature of the reduced [W 10 O 32 ] 6À template and the effective silver-oxygen interaction contribute to the formation of the Ag 44 nanowheel in 1. The luminescence, photocatalytic activity and electrochemistry properties of 1 were studied.[a] J.