Abstract Cationic polymers, which are commonly used as flocculants and coagulant aids in water and wastewater treatment, have been recently reported to promote the formation of nitrosamines. Most of the findings to date are based on poly (epichlorohydrin dimethylamine) and poly (diallyldimethylammonium chloride), while few studies have considered nitrosamines formation of polyacrylamides. In this work, the nitrosamines formation from non-ionic, anionic and cationic polyacrylamides was evaluated. Moreover, the effects of chemical structures of cationic polyacrylamides (including molecular weight, charge density, and monomers) on nitrosamines formation were investigated. The results revealed that the highest amount of nitrosamines formation was formed from cationic polyacrylamide, followed by non-ionic polyacrylamide and anionic polyacrylamide. Molecular weight and various cationic monomers showed no significant effects on nitrosamines formation, but monomers generated significantly higher amount of nitrosamines formation than cationic polyacrylamides. Nitrosamines formation increased with the increasing charge density of cationic polyacrylamides, and FTIR analysis results showed that the quaternary amine groups preferentially reacted with chloramines than with amide groups. This work shed new light on the nitrosamines formation from water and wastewater treatment polymers. Graphical abstract Unlabelled Image Highlights • The highest nitrosamines formation occurred at CPAM, followed NPAM and APAM. • Molecular weight and various cationic monomers of CPAM have no obvious effect on nitrosamines formation. • Quaternary amine groups of CPAM were easier to react with chloramines than amide groups [ABSTRACT FROM AUTHOR]