Low-humidity sensors were made by layer-by-layer (LBL) self-assembly of poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA) or poly(styrenesulfonic acid) sodium salt (PSS) and poly(allylamine hydrochloride) (PAH) into multilayer thin films on a gold electrode of quartz crystal microbalance (QCM). The thin films were characterized by QCM and atomic force microscopy (AFM). The effects of maleic acid (MA) in PSSMA, the number of layers and the ionic strength on the low-humidity sensing properties (sensitivity) were compared with those of PSS. The sensitivity of the PSSMA/PAH multilayer thin film exceeded that of the PSS/PAH multilayer thin film when the multilayered thin films of polyelectrolytes were prepared from solutions without NaCl. The sensitivity of both PSSMA/PAH and PSS/PAH multilayered thin films was increased by increasing the number of layers and by adding salt to the deposition solution. The PSS/PAH multilayered thin film that was prepared from the solutions with NaCl had the highest sensitivity (1.923 −ΔHz/Δppmv at 27.5 ppmv) and a short response time. Spin-coating was also adopted to fabricate PSS-based low-humidity sensors for comparison.