Triclosan is a commonly used biocide effective against bacterial and fungal infections. However, its overuse in pharmaceutical and personal care products has resulted in its abundance in the natural environment. The detection of triclosan by visual spectroscopy can be carried out using the azo-coupling reaction of diazonium complexes. However, the reaction is also common to other phenolic compounds and aromatic amines, posing significant challenge. In this work, we investigate the azo-coupling reaction of triclosan and several commonly occurring analogous compounds to develop an improved spectroscopic method for the selective determination of triclosan without interference. We find that the azo-coupling reaction between the diazotized derivative and the phenolic compounds is highly dependent on the pH of the reaction media. At pH 7.2, the absorbance of the azo dye product of triclosan shows a peak at 452 nm which has minimal interference from other phenolic azo-dye products with the exception of naphthol. Naphthol shows an interference corresponding to 58% of the analytical signal of equimolar triclosan concentration. To overcome this, we develop an analytical model for the simultaneous determination of triclosan and naphthol from mixed solutions of the compounds. A linear calibration plot from 1.7 to 34 µM was obtained for both triclosan and naphthol with limit-of-detection (LOD) of 0.62 µM and 1.03 µM respectively. The developed protocol was tested for the analysis of water samples collected from various environmental sources spiked with different concentrations of triclosan and naphthol. The samples were enriched by solid-phase-extraction which allowed a 50-fold enhancement in detection of triclosan. The average relative recovery of triclosan in real samples was found to be 98.6%. © 2021 Elsevier B.V.