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The controlled/living free-radical copolymerization ofvinylidenechloride (VDC) with methyl acrylate (MeA) or acrylic acid (AA) wasstudied by the reversible addition–fragmentation chain transfer(RAFT) technique using a trithiocarbonate RAFT agent. The reactionswere performed in 1,4-dioxane solution at 30 °C and led to goodcontrol and high chain-end functionality. P(VDC-co-MeA)-b-PAA, PAA-b-P(VDC-co-MeA), and PAA-b-P(VDC-co-AA) amphiphilic block copolymers were then prepared in the sameconditions, starting either from a hydrophobic P(VDC-co-MeA) macromolecular RAFT (macro-RAFT) agent or from a hydrophilicPAA one. The advantage of the first synthesis pathway relies on thevery good transfer efficiency to trithiocarbonate-ended P(VDC-co-MeA) and on the rapid consumption of the latter evenwhen low percentages (10 mol %) of MeA comonomer are incorporatedin the macro-RAFT agent. In contrast, for the second approach a rapidconsumption of the macro-RAFT agent is only reached with 30 mol %of MeA in the comonomer feed, whereas with 10 mol % of MeA the transferconstant was determined to be only close to 1. Finally, we demonstratedthat PAA-b-P(VDC-co-AA) diblockcopolymers might also be obtained with controlled features in a one-potprocess. [ABSTRACT FROM AUTHOR]