Sulfite is a very important species, affecting human health, plant and animal life, and environmental sustainability. In this study, for the first time, an ionophore-based ion-selective optode was constructed for hydrogen sulfite determination in beverages, such as Birell® and Sprite®, water, and soil samples; instead of normal pH-chromoionophores, polyaniline film was precipitated on a glass slide and used for the transduction of the sensation mechanism. The ionophore-modified polyaniline-based optode incorporated thiourea derivative as an ionophore and tridodecyl methyl ammonium chloride as an ion-exchanger. The optode film was prepared in situ with a modified chemical polymerization method, and it was characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM), and X-ray diffraction (XRD); also, FTIR spectroscopy was performed for the film before and after interaction with hydrogen sulfite for mechanism elucidation. The optode was applied in the hydrogen sulfite concentration range of 10-1 to 10-5 M with a low detection limit of 8.0 × 10-6 M and minimum interference of other interfering species, such as salicylate, iodide, and sulphide. The response mechanism was due to the ion-exchange of hydrogen sulfite with the anion exchanger, followed by the molecular recognition between thiourea ionophore and hydrogen sulfite, with concomitant redox reaction via the protonation of the polyaniline that causes a decrease in absorbance at 685 nm. The optode was applied successfully for the determination of hydrogen sulfite in real beverages, Birell® and Sprite® without any pretreatment steps. Also, it was applied successfully for the environmental monitoring of hydrogen sulfite in real wastewater and soil samples.