Thioacrylates are a novel class of monomers that have been shown to be polymerisable. However, knowledge of their polymerisation behaviour in metal mediated radical polymerisation is limited, although the thioester functionality allows efficient post modifications. In this report, findings on the polymerisation of thioacrylates via SET-LRP conditions are presented. In a set of carefully monitored optimisation reactions, low conversions were observed when CuBr 2 was employed, which is due to the complexation of the thioester with Cu catalyst. Nevertheless, once CuBr 2 is replaced with an iron based deactivator, full conversion for the homopolymerisation of ethyl thioacrylate is achieved. In a next step, the polymerisation conditions for an ethyl thioacrylate and a methyl acrylate block copolymer are optimised. The obtained block copolymer was subjected to an amidation reaction to obtain an all-acrylic copolymer, consisting of an acrylate, a thioacrylate and an acrylamide. Ethyl thioacrylate was polymerised via Cu-RDRP and subjected to amidation to obtain the first "all-acrylic" copolymer.