AbstractThe importance of polycarboxylate ethers (PCE) as concrete superplasticizers has significantly increased in recent decades, both technically and commercially. At the least, three descriptors describe the average PCE structure: the side chain length (P), the charge density (N), and the number of repeating units (n). The synthesis parameters determine the average composition of the PCEs and, consequently, their performance in cementitious materials. This study examines the rheological properties of 27 different PCE structures, which were synthesized using redox‐initiated free‐radical copolymerization. We independently varied the parameters P and N and produced three PCEs with different molar weights for each combination of P and N. Cement pastes with low PCE dosages of 0.035 wt% were tested in a rheometer using a plate‐plate geometry. It turns out that when the PCE is added directly to the mixing water, the PCE has a complex influence on the very early hydration. Consequently, the obtained rheology data is not entirely in line with available structure‐activity relationships. Additionally, we attempted to model the observed rheology data based on three structural PCE descriptors. While a multivariate linear regression model failed to accurately describe the relationship, a random forest model delivered a better model. In summary, we conclude that the impact of PCEs on early hydration significantly affects the rheology of the paste. The changed hydration pathway causes a deviation of our results from existing structure‐activity relationships and makes it challenging to statistically model the sparse rheology data with a minimal set of three structural descriptors.