The optical ammonia-sensing properties of water-dispersible polyaniline (PANI) complexes chemically synthesized in the presence of polysulfonic acids of different structure and chain flexibility were compared for the first time. Flexible-chain poly(styrene-4-sulfonic acid) and poly-(2-acrylamido-2-methyl-1-propanesulfonic acid), as well as semi-rigid-chain poly-4,4′-(2,2′-disulfonic acid)diphenylene-iso-phthalamide and rigid-chain poly-4,4′-(2,2′-disulfonic acid)diphenylene-tere-phthalamide (t-PASA) were used. The sensor films were prepared by a convenient and scalable method—spray coating of aqueous solutions on glass substrates. The optical response time and amplitude of the sensor films in the range of ammonia concentrations from 5 to 200 ppm were investigated. To overcome the influence of humidity and presence of over-stoichiometric protons of the polyacid on the accuracy of ammonia determination treatments of the films in aqueous solutions of NaCl, CaCl₂ and BaCl₂ were tested. The treatment in 1 M CaCl₂ solution for all of the PANI complexes results in a significant improvement in the response time, amplitude and reproducibility. The films of PANI complexes with the flexible-chain polyacids have the highest response amplitude in the range of ammonia concentrations 5–25 ppm. PANI-t-PASA film demonstrated the best sensory properties at ammonia concentrations more than 50 ppm. FTIR spectroscopy showed that CaCl₂ treatment results in cross-linking of sulfoacid groups from adjacent polyacid chains by Ca²⁺ ions. Thus, such a treatment results both in the neutralization of excessive protons and a significant reduction in the films’ swelling at high humidity.