Summary: The first example of a room temperature reversible addition‐fragmentation chain transfer polymerization conducted directly in aqueous media is detailed. Under these conditions acrylamide and N,N‐dimethylacrylamide may be polymerized in a controlled fashion to near quantitative conversions employing a difunctional trithiocarbonate chain transfer agent (CTA). Hydrolysis studies conducted at pH 5.5 suggest that the CTA is stable up to approximately 50 °C.