Aqueous solutions of sodium acetate (CH3COONa) and potassium acetate (CH3COOK) are considered effective alternative heat exchange media for frost-free air–source heat pumps (FFASHPs) owing to the low corrosiveness, low viscosity, and low cost. Equilibrium vapor pressure is the most crucial property that characterizes freezing point and latent heat transfer. However, studies on this property, especially in subzero temperature ranges are scarce. This study was conducted to experimentally investigate the equilibrium vapor pressure of CH3COONa and CH3COOK solutions. The developed apparatus and procedures were based on the static method, and validated by evaluating the vapor pressure of distilled water, n-heptane, and calcium chloride (CaCl2) aqueous solution. Their average absolute deviations were within 1.94%. As the temperature increased from 263 to 328 K and solute concentration increased from 9.27 to 33.81 wt%, 124 data points of the vapor pressure of the CH3COONa and CH3COOK solutions were obtained, ranging from 0.2759 to 13.2608 kPa. Modified Antoine equation and ion interaction (Pitzer) model were established for correlation of the experimental data. The average absolute deviations of the CH3COONa and CH3COOK solutions produced by Antoine equation were 2.08 and 2.48%, respectively. Those produced by Pitzer model further decreased to 1.36 and 1.45% due to the import of osmotic coefficient and the accuracy improvement. Furthermore, according to the experimental and calculation results, the vapor pressure of the CH3COONa solution was lower than that of the CH3COOK solution. Therefore, under the same antifreezing conditions, the CH3COONa solution facilitates latent heat absorption from ambient air, while the CH3COOK solution is conducive to achieve regeneration. The results of this study provide foundational data for the vapor pressure of the two solutions and can promote their application in FFASHPs.