Waterborne polyurethane‐block‐polystyrene latexes were prepared by miniemulsion polymerization in a single batch. A direct miniemulsion of the monomers mixture containing styrene, IPDI, 2,4‐diethyl‐1,5‐pentanediol and a diol‐functionalized azoinitiator was prepared in water. The polyaddition reaction of the PU was then performed in a first step at room temperature, with the help of the catalysts mixture DBTDL/DMDA, yielding a PU macroazoinitiator. In a second step, the miniemulsion was heated to 72 °C to start the radical polymerization of styrene from the macroazoinitiator chains. The polymers obtained from the miniemulsion were fractionated and each fraction was analyzed by GPC, DSC and 1H NMR spectroscopy. It was shown that 45% of a (linear) copolymer consisting of a PU and PS was obtained, which is a good compatibilizer for PU/PS polymer blends. TEM from the polymer particles in miniemulsion revealed a homogeneous structure inside the particles.magnified image