AbstractWhen used by itself, polyethylene imine (PEI) does not perform well as cement fluid loss additive. Its combination with acetone formaldehyde sulfite (AFS) polycondensate, however, exhibits excellent filtration control. The mechanism underlying this synergistic effect was studied and the conditions producing best results were determined. For optimum performance, PEI and AFS must be reacted with each other to yield a polyelectrolyte complex (PEC) (d ∼ 5–10 μm), which effectively plugs the pores of the cement filter cake. Composition, size, and effectiveness of the PEC are strongly influenced by the anionic charge amount of the AFS dispersant. Ionic interactions between cationic imine functionalities of PEI and anionic sulfonate groups existing in AFS were confirmed by conductivity, infrared, zeta potential, and particle size measurements. For AFS samples possessing different degrees of sulfonation, the largest particle size and hence best fluid loss performance of the PEC was found to occur at a PEI:AFS molar ratio, which corresponds to neutral charge. Occurrence of large PEC particles (d ∼ 5 μm) within the cement filter cake pores was visualized by scanning electron microscopy, and their stability in highly alkaline cement pore solution was confirmed by particle size measurement. Other anionic polyelectrolytes may be used to yield such PECs with PEI to provide effective fluid loss control for cement slurries. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011