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A novel optical probe has been successfully developed for the selective detection of Os(VIII) ions. This osmium-sensing platform was intricately designed by incorporating 4-(thiazol-2-yldiazenyl)benzene-1,3-diol (TDBD) as the ionophore within a plasticized PVC membrane, and tributylphosphate (TBP) serving as the plasticizer. Upon exposure to Os(VIII) ions in a 0.5 M HClO4 acid milieu, the sensing membrane undergoes a distinctive chromatic transition, shifting from a yellow to a pink hue. The preparation of the sensor and the methodology for Os(VIII) determination were meticulously refined to achieve optimal performance. Under these carefully optimized experimental conditions, the proposed optode demonstrated an impressive linear detection range spanning from 2.5 × 10−9 to 2.5 × 10−5 M for Os(VIII), alongside remarkable detection and quantification limits of 7.24 × 10−10 and 2.4 × 10−9 M, respectively. The sensor consistently delivered highly reproducible results, as evidenced by relative standard deviation (RSD) values of 1.45% and 1.30% for Os(VIII) concentrations at 7.5 × 10−7 and 2.5 × 10−6 M, respectively, underscoring its precision and reliability. Furthermore, the sensor exhibited a swift response time of 3.0 min, further emphasizing its efficiency. The incorporation of PIMs into the sensor architecture led to a remarkable eight-fold enhancement in its response compared to counterparts lacking PIMs, signifying a significant performance improvement. In assessing potential interference, an investigation into the influence of other ions on Os(III) determination revealed that the prepared sensor displayed exceptional selectivity for Os(VIII) ions, with negligible responses observed in the presence of common ions. Collectively, these experimental findings underscore the sensor's efficacy as an invaluable tool for the precise analysis of osmium content in water samples, aligning it with the rigorous standards of international scientific research.