PolyCarboxylate ether-based superplasticizers (PCEs) are a type of comb-shaped copolymers used as polymeric dispersants in cementitious materials. PCEs have a high degree of dispersity, which limits the suitability of conventional characterization techniques, such as Size Exclusion Chromatography (SEC). Properties of PCEs strongly depend on their molecular structure and a comprehensive characterization is needed to fully understand the structure–property relationships. PCEs with well-defined molecular structures were synthesized to study their solution conformation by SEC and scattering techniques. The combined use of SEC, dynamic light scattering and small-angle neutron scattering allowed us to demonstrate the validity of a scaling law describing the radius of gyration of comb-shaped copolymers as a function of their molecular structure. Moreover, we show that the use of SEC with standard calibration, although widely spread, is not adequate for PCEs.