Polyacrylamide (PAM) and its derivatives are the most commonly used polymers in the preparation of polymeric gels for water control in petroleum reservoirs. This study involved the use of polyethylenimine (PEI) as a crosslinker for PAM. In this study, we investigated PAM alkaline hydrolysis at high temperatures. The effects of salts [sodium chloride (NaCl) and ammonium chloride (NH4Cl)] on the degree of hydrolysis (DH) of PAM were investigated. These salts were used as retarders to elongate the gelation time of the PAM/PEI system. The data obtained from 13C‐NMR was used to understand the retardation mechanisms by salts. We found that NH4Cl accelerated the extent of hydrolysis more in comparison with NaCl. Moreover, the apparent viscosity of the hydrolyzed samples was measured. PAM hydrolysis in the presence of NH4Cl resulted in a lower solution viscosity than that in the presence of NaCl. Therefore, NH4Cl was more effective in shielding negative charges on the carboxylate groups of the partially hydrolyzed polyacrylamide (PHPA) chain. NaCl and NH4Cl were compatible with the PHPA/PEI system, but sodium carbonate showed a white precipitate. In addition, high‐temperature/high‐pressure elastic modulus data were reported for the first time for this system. Differential scanning calorimetry was coupled with rheology to explain the PAM/PEI crosslinking in the presence of salts. Models were developed to assess the impact of the salts on the PAM DH and the induction period before gelation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41185.