A one‐pot solution polymerization under mild conditions was adapted for the synthesis of well‐defined aliphatic‐aromatic polyesters with different degrees of branching. The esterification was performed at room temperature using 4,4‐bis(4′‐hydroxyphenyl)valeric acid (AB2) and 3‐(4‐hydroxyphenyl)propionic acid (AB) as monomers. DPTS was used as a catalyst and DCC as a coupling agent. Polyesters with statistical, dendritic topology, controlled degree of branching and $\overline M _{\rm w}$ > 35 000 g · mol−1 were obtained. The polymers were characterized by 1H and 13C NMR, SEC, DSC, and TGA. A strong dependence of the degree of branching and the thermal properties of the polymers depending on the AB/AB2 monomer ratio was observed.magnified image