Water‐soluble synthetic transition metal catalysts have been studied extensively for many reactions, but for olefin polymerization such catalysts have been lacking. We report herein a straightforward synthesis of phosphinephenolato NiII catalysts endowed permanently with a hydrophilic sulfonate moiety bound to the chelating ligand. These catalysts’ hydrophilic active sites promote aqueous ethylene polymerization with high activity (TOF up to 6.3×104 molEthylene molNi−1 h−1) to high molecular weight polyethylene (HDPE), with half‐lives on the order of hours also at elevated temperatures. The obtained polyethylene dispersions feature narrow particle size distributions without any aggregates.