Hypervalent (HV) iodine(III) compounds with fluorine-containing ligands (F, CF3, C6F5CO2, or CF3(CF2)(8)CO2 (n-C9F19CO2)) reacted, in the presence of iodine or copper salts, with the double bonds in cis-1,4-polyisoprene (polyIP) to afford fluorine-containing polymers. For instance, fast iodo-fluorination of polyIP was accomplished in the presence of 4-(difluoroiodo)toluene (4-TolIF(2)) and iodine. The reaction of polyIP with 1-trifluoromethyl-1,2-benziodoxol-3(1H)-one (Togni reagent II) and copper(I) iodide under mild conditions yielded polymers with vicinal pendant trifluoromethyl and 2-iodobenzoate groups, which were subjected to acid-promoted elimination to give a fluorine-containing unsaturated polymer. The simultaneous introduction of trifluoromethyl groups and a halogen (Cl or Br) was achieved by reacting polyIP with Togni reagent II in the presence of thionyl halide and copper(II) salts. The alkyl chloride pendant groups in the product of the copper-mediated reaction of polyIP with thionyl chloride and Togni reagent II were subsequently converted to azide functionalities by nucleophilic substitution with NaN3, and the produced azide-containing polymer was subjected to copper(I)-catalyzed "click" coupling reaction with a fluorescent alkyne, propargyl 4-(1-pyrenyl)butyrate. Perfluoroacyloxy pendant groups were also introduced successfully by the reaction of polyIP with HV iodine(III) reagents with perfluorinated carboxylate ligands, i.e., C6H5I(O2CC6F5)(2) and C6H5I(O2C(n-)C9F19)(2), in the presence of iodine. No significant chain degradation and/or cross-linking was observed in any of the functionalization reactions. The modified polymers showed relatively good thermal stability and high hydrophobicity, with contact angles toward water in the range of 89-116 degrees.