Novel CO 2 -philic Pd complexes, PdCl 2 [4,4'-bis(R f CH 2 OCH 2 )-2,2'-bpy] (bpy: 2,2'-bipyridine) where R f = n-C 10 F 21 , n-C 11 F 23 , were anchored onto a silica support modified with long fluorinated hydrocarbon chains (C 6 F 13 ) by mixing these complex and the support in DMSO at 413 K. These immobilized Pd complex catalysts were applied for the photoreduction of CO 2 in DMF or organic solvents using triethylamine as a hydrogen donor at 323 K. The rate of CO 2 reduction and the selectivity to CO were observed to depend on several factors including CO 2 pressure, solvent, Pd complex structure, and Pd loading. With the most active catalyst, the selective photoreduction of CO 2 to CO can be achieved in DMF at a CO 2 pressure of 4 MPa and the performance observed is much better compared to the literature results. The features of the supported 2 Pd complexes and the multiphase reaction media were characterized by UV-Vis absorption and others to discuss the reasons for their high performance.