Abstract: Linoleic acid modified with auto-oxidation, hydroxylation, bromination and azidation was used to synthesis graft copolymers using ω-alkyne-terminated poly(ε-caprolactone) (alk-PCLs) via "click" reaction. In the first step, the polymeric linoleic acid (PLina) as macroinitiator was obtained by the autoxidation of linoleic acid. Hydroxylation of the PLina was then carried out using diethanolamine to produce hydroxylated polymeric linoleic acid (PLina-OH). The PLina-OH was chem. modified with 2-bromopropionyl bromide to obtain bromo-functionalized polymeric linoleic acid (PLina-Br). This macroinitiator was then modified with sodium azide, resulting in azide polymeric linoleic acid (PLina-N3). In a parallel process, ω-alkyne-terminated poly(ε-caprolactone) (alk-PCLs) were prepared via ROP of the ε-caprolactone monomer in the presence of propiolic acid, 3-butyn-1-ol, 5-hexynoic acid, and propargyl alc. as the precursors and tin(II) 2-Et hexanoate (Sn(Oct)2) as the catalyst. These preliminary steps involved the synthesis of azide and alkyne compounds capable of being linked together via the alkyne-azide cycloaddition reaction catalyzed by copper (Cu(I)), which led to poly(linoleic acid)-g-poly(ε-caprolactone) (PLina-g-PCL). The obtained polymers were characterized by proton NMR (1H NMR), Fourier-transform IR (FTIR), differential scanning calorimetry (DSC), thermal gravimetric anal. (TGA) and elemental anal. Graphic abstract: JCSC-D-21-00100 [graphic not available: see fulltext]