In order to study the solution properties of polyacrylamide at high temperatures at the molecular-atomic scale, the molecular models of partially hydrolyzed polyacrylamide (HPAM) and AM/AANa/AMPSNa copolymer [P(AM/AANa/AMPSNa)] have been established through a combination of experimental methods and molecular dynamics simulations. The solution properties of the two polymers at elevated temperatures were systematically investigated in terms of polymer chain rigidity and flexibility, hydrogen bonding, hydration layer, interaction energy and the effect of salt cation, and the micro-mechanism of temperature resistance of P(AM/AANa/AMPSNa) was explained. The results show that the introduction of side chains containing methyl and sulfonated groups into the molecular chain of P(AM/AANa/AMPSNa) could increase the rigidity of the molecular chain, more hydrogen bonds are formed between sulfonated groups and water and has longer lifetime. At the same time, the strong polar sulfonic acid group makes the hydration layer denser, which results in the weaker static shielding effect of the cations on the P(AM/AANa/AMPSNa). Under different temperature conditions, P(AM/AANa/AMPSNa) has stronger intermolecular non-bonding interactions, stronger water retention effect of the molecular chain at the microscopic level, and higher viscosity at the macroscopic level.