Hyperbranched copolymers were prepared by the heat transesterification of 4-hydroxycinnamic acid (4HCA) and 3,4-dihydroxycinnamic acid (DHCA) with a high 4HCA composition dissolved in trifluoroacetic acid (TFA). The nanoparticles were formed after two homogeneous copolymer solutions were mixed in DMF and TFA, which are both good solvents for the copolymer P(4HCA-co-DHCA). We confirmed that the driving force for particulation was solvent interactions that produce ion pairs, which elevate the polarity of the solvent too much to solubilize the copolymers.