Hydrogen-bonded complexation between high-molecular-weight poly( N -vinylpyrrolidone) (PVP, M -w = 650 kDa) and poly(acrylic acid) (PAA) with weight-average molar weights between 0.9 and 50 kDa, is studied in dilute, salt-free aqueous solution. The onset of complexation, aggregation, and the structure of the formed particles are strongly infl uenced by PAA molecular weight, solution composition, and the method of sample preparation. With increasing poly(acrylic acid) chain length, IPCs show higher stability against aggregation. IPCs based on high-molecular-weight PAA show core-corona architecture ensuring good sterical stabilization, whereas for those containing the shortest polyacid a loose soft-sphere structure without distinct borders of different chain densities is found.