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The effect of molecular architecture, star versus linear, poly(ethylene oxide) (PEO) on the formation of hydrogen‐bonded complexes with linear poly(methacrylic acid) (PMAA) is investigated experimentally and rationalized theoretically. Isothermal titration calorimetry reveals that at pH 2.5 interpolymer complexes (IPCs) of PMMA with a 6‐arm star PEO (sPEO) contains ≈50% more polyacid than IPCs formed...