The fluorous PtCl2[5,5′-bis-(n-C11F23CH2OCH2)-2,2′-bpy] complex (2) was prepared and employed as recoverable catalyst for the hydrosilylation of alkynes. Pt-catalyst 2 with F-content 0.53 was recovered under the thermomorphic method by design and the catalyst was demonstrated capable of re-usage for 8 times without loss of activity. The leaching of Pt in product mixture was monitored, with ICP-MS, to be at as low as 10−6 level per cycle in the 5-decyne reactions and at 10−3 level per cycle in the (HO)CMe2CCH reaction. The reaction-catalyst fulfills the principle of green chemistry, and with its addition nature the hydrosilylation delivers 100% atom economy. The easily prepared polyfluorinated (2,2′-bpy)Pt complex 2 is the robust and thermally stable catalyst, which doesn't require specific handling for utilization and storage in laboratory.