The study of perfluoroalkyl metal complexes is key to understanding and improving metal-promoted perfluoroalkylation reactions. Herein we report the synthesis of the first gold complexes with primary or secondary perfluoroalkyl ligands by photoinitiated reactions between Au(I) organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuRF (L = PPh3 or N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; RF = n-C4F9, n-C6F13, i-C3F7, c-C6F11) and [Au(RF)(Ar)I(PPh3)] (Ar = 2,4,6-trimethylphenyl) have been isolated and characterized. Alkynes RFC≡CR were formed by reaction of Ph3PAuC≡CR (R = Ph, nHex) with IRF (RF = n-C4F9, i-C3F7). Evidences of a photoinitiated radical mechanism for these reactions have been obtained. Au(III) complexes [Au(n-C4F9)(X)(Y)L] (X = Y = Cl, Br, I, Me; X = Me, Y = I) have been prepared or in situ generated, and their thermal or photochemical decomposition reactions have been studied