In this study, polyacrylic acid (PAA) films were deposited onto a quartz surface acoustic wave (SAW) resonator using a spin-coating technique for ammonia sensing operated at room temperature, and the sensing mechanisms and performance were systematically studied. The oxygen-containing functional groups on the surfaces of the PAA film make it sensitive and selective to ammonia molecules, even when tested at room temperature. The ammonia molecules adsorbed by the oxygen-containing functional groups of PAA (e.g., hydroxyl and epoxy groups) increase the membrane’s stiffness, which was identified as the primary mechanism leading to the positive frequency shifts. However, mass loading due to adsorption of ammonia molecules is not a major reason as it will result in a negative frequency shifts. When the PAA coated SAW sensor was exposed to ammonia with a low concentration of 500 ppb, it showed a positive frequency shift of 225 Hz, with both good repeatability and stability, as well as a good selectivity to ammonia compared with those to C2H5OH, H2, HCl, H2S, CO, NO2, NO, and CH3COCH3.