Summary: ATRP of butyl α‐fluoroacrylate (FABu) was carried out at 90 °C using methyl 2‐bromoisobutyrate (2‐MBiB) as initiator and the homogeneous catalyst CuBr/1,1,4,7,10,10‐hexamethyltriethylenetetramine (HMTETA). Telechelic oligomers were obtained by coupling the bromo terminated polymers in the presence of Cu(0) and 2,2′‐bipyridyl ligand. The 1H and 19F NMR, SEC and MALDI TOF analyses show that the poly(FABu) chains recombination was the main reaction (80% yield). About 20% of disproportionation reaction also occurs in the process, whereas transfer reactions can be neglected.