Glass polyalkenoate cements (GPCs) have been used in dentistry for over 40 years. These novel bioactive materials are the result of a reaction between a finely ground glass (base) and a polymer (acid), usually poly (acrylic acid) (PAA), in the presence of water. This article reviews the types of PAA used as reagents (including how they vary by molar mass, molecular weight, concentration, polydispersity and content) and the way that they control the properties of the conventional GPCs (CGPCs) formulated from them. The article also considers the effect of PAA on the clinical performance of CGPCs, including biocompatibility, rheological and mechanical properties, adhesion, ion release, acid erosion and clinical durability. The review has critically evaluated the literature and clarified the role that the polyacid component of CGPCs plays in setting and maturation. This review will lead to an improved understanding of the chemistry and properties of the PAA phase which will lead to further innovation in the glass-based cements field