[{Cp*Rh(S2C6H4)}(2)W(CO)(2)] (Cp*: eta(5)-C-5-Me-5) (1) and [{Cp*Rh(S2C6H4)}(S2C6H4)W(CO)(2)] (2) were synthesized by the reaction of rhodadithiolene [Cp*Rh(S2C6H4)] with [W(CO)(3)(py)(3)], and their crystal structures and physical properties were investigated. The formation mechanism of 2 from 1 was pursued by H-1 NMR spectroscopy. 1 reacted with an excess amount of BF3 center dot Et2O to furnish 2, indicating that a Lewis acid assisted the demetalation reaction.