Copper(I)-mediated heptafluoroisopropylation of aryl halides (ArX: X = I, Br) is demonstrated using copper(I) carboxylates and a bis(heptafluoroisopropyl)zinc reagent Zn( i-C3F7)2(dmf)2, prepared from heptafluoroisopropyl iodide and diethylzinc. The air-tolerant solid heptafluoroisopropylzinc reagent is advantageous to conduct simple synthetic operations and successful to give the corresponding heptafluoroisopropyl arene derivatives via transmetalation to copper(I) center. The newly developed copper(I)-mediated heptafluoroisopropylation process can be advanced to the copper(I)-catalysis by silver carboxylate salts and complementary to the precedent radical-based processes.