In this study, we report the use of a double-headed dialkoxyamine trithiocarbonate (I) capable of acting as chain transfer agent via reversible addition-fragmentation chain transfer polymerization or as initiator via nitroxide-mediated polymerization. It is worth mentioning that I was revealed as an effective dual chain transfer agent in the synthesis of multi-block copolymers via bulk and emulsion processes. In this article, we report the employing of I in dispersed systems to obtain amphiphilic multiblock copolymers and latexes. In this case, a water soluble macroagent of PAA previously synthetized was used in disperse media using a mixture of methanol/water (70: 30, w/w). Stable latexes were obtained via polymerization-induced self-assembly and surface-initiated polymerization of SSNa from alkoxyamine-functionalized latex PAA-b-PS-b-PAA was also obtained (C) 2016 Wiley Periodicals, Inc.