In this work, a new polymeric dispersants based on poly[oligo(ethylene oxide) methyl ether acrylate] (POEOA) as hydrophilic block and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and dopamine (Dopa) as anchoring molecules, have been synthetized and successfully used as efficient tailor-made polymers for the aqueous dispersion of titanium dioxide (TiO₂) particles. The controlled structure of this new class of additives was obtained by initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP). The proposed polymer dispersants were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance analysis (¹H NMR). The dispersion efficiency was evaluated by dynamic light scattering (DLS), zeta potential (ζ), rheology and transmission electron microscopy (TEM). The influence of different stabilizing blocks bounded to the same anchoring block on the dispersion efficiency was evaluated in aqueous dispersions of TiO₂ using a common water-based paint formulation (satin vinyl paint). Aiming for industrial validation, a satin paint was also formulated with the new dispersants. Higher gloss (up to 39%) and improved pigment dispersion were observed when using the tailor-made polymers, comparing to the use of a standard commercial poly(acrylic acid) (PAA) dispersing agent. The data presented suggest that POEOA-based macrostructures are highly efficient additives for the dispersion of TiO₂ in water-based paint formulations.