AbstractPoly(caprolactone) (PCL) was blended with poly(chlorostyrene) (PSCI) and chlorinated polypropylene (PPCl). A single glass transition temperature Tg was found for these mixtures, indicating their miscibility. PCL crystallizes in these blends when the chlorinated polymer content is not too high. Otherwise, Tg becomes higher than the melting point of PCL and the high viscosity of the medium hinders the crystallization. The miscibility of PCL/PPCI blends cannot be due to hydrogen bonding between the α‐hydrogens of the chlorinated polymer and the carbonyl group of the polyester since PPCI does not have available a large number of α‐hydrogens. It is suggested that a dipoledipole CO…ClC interaction is responsible for the observed miscibility phenomenon and that this interaction is probably also responsible for the miscibility between all other polyesterchlorinated polymer mixtures. Finally, it was observed that poly(α‐methyl‐α‐n‐propyl‐β‐propiolactone), poly(α‐methyl‐α‐ethyl‐β‐propiolactone) and poly(valerolactone) are not miscible with PSCI or PPCl, despite the fact that they are miscible with poly(vinyl chloride).