Polymeric linoleic asit graft copolymers were synthesized via a nitroxide-mediated radical polymerization (NMRP) method in the presence of 2,2-6,6-tetramethylpiperidinyl-1-oxy (TEMPO). For this purpose, PLina-ox was exposed to polymerization with styrene (Sty) or Sty and pentafluorostyrene (F 5 Sty) in the presence of TEMPO by NMRP method in order to obtain PLina-g-PSty and PLina-g-PF 5 Sty-g-PSty graft copolymers with controlled structure and low polydispersity. Chain extension study was evaluated. Principal parameters, such as monomer concentration, initiator concentration, and polymerization time, which effect the polymerization reactions, were evaluated. The products thus obtained were well characterized by 1 H NMR, GPC, and 19 F NMR measurements.Practical application: We report for the first time the synthesis of PLina-g-PSty and PLina-g-PSty-g-PF 5 Sty graft copolymers in the presence of TEMPO. NMRP reactions were performed in the presence of TEMPO in order to obtain graft copolymers with controlled molecular weight and polydispersity. Chain-extension reactions were also successfully carried out because of the activation of TEMPO terminated chain ends of graft copolymers. Pure linoleic acid was auto-oxidized under daylight and air oxygen, yielding peroxidized PLina (PLina-ox). PLina-ox has been used in the polymerization of styrene (Sty) or copolymerization of Sty and pentafluorostyrene (F 5 Sty).