A low-molar mass poly(acrylic acid) with narrow molar-mass distribution prepared by SCl nitroxide-mediated controlled free-radial polymerization, was subjected to end-group analysis to confirm its living nature, H-1 and P-31 NMR spectroscopy confirmed the presence of the SG1-based alkoxyamide end group. Futhermore, chain extension with styrene and n-butyl acrylate demonstrated the ability of the homopolymer to initiate the polymerization of a second block. These results open the door to the synthesis of poly(acrylic acid)-based block copolymers by direct nitroxide-mediated polymerization of acrylic acid.