Aqueous foam is widely used in fire extinguishing and dust suppression technologies. Improving the foaming ability is the key to reducing the added concentration of foaming agents as well as the economic cost. In this work, the effect of a water-soluble polymer (polyvinyl alcohol, PVA) on the foaming ability of anionic surfactant (sodium dodecyl ether sulfate, SDES) was studied by an experiment and molecular dynamics simulation. The experimental results showed that PVA greatly improves the foaming ability of SDES solutions when the surfactant concentration is less than 0.1%, which is attributed to the fact that the polymer can enhance the stability of bubble films and reduce the bubble rupture rate during the foam generation process. The simulation results indicate that PVA can enhance the hydration of surfactant head groups and contribute to the formation of a three-dimensional hydrogen bond network between surfactants, polymers, and water molecules, thus greatly improving the stability of bubble liquid films. The above results suggest that water-soluble polymers can be used to improve the foaming ability of surfactant solutions by enhancing the bubble film stability, which is beneficial as it reduces the added concentration of foaming agents in aqueous foam applications.