AbstractWithin the scope of this study, the effect of the main chain length of polycarboxylate-based water-reducing admixture (WRA) on the fresh properties, compressive strength, and water absorption of mortar mixtures containing fly ash was investigated. Three WRAs with the same structure but different main chain lengths and resultantly different molecular weights were used. Effects of the admixtures on the properties of cementitious systems with 0, 15, 30, and 45 wt.% fly ash were investigated. Irrespective of the fly ash substitution level, the fluidity of the mixtures was improved when the admixture main chain length was increased up to a certain level. Possibly beyond a certain main chain length, the entanglement of too large main chains of the polymer to each other reduced the electrostatic effect of the polymer. Thus, the flow properties of the mixtures were affected negatively. The side chain molecular weight (length) of the admixtures was fixed (2,400 g/mol). However, the molecular weight of the admixtures was adjusted as 24, 48, and 71 kg/mol by changing the main chain length of the polymer. The admixture with 48 kg/mol molecular weight showed the best performance in terms of mortar fresh properties. However, the change in the length of the main chain of admixture did not have a considerable effect on the compressive strength and water absorption of the mortar. In addition, apart from the WRA admixture property, time-dependent flow and permeation properties of the mixtures were affected negatively by the increase in fly ash substitution level.