A novel method has been developed for accurately quantifying arsenic species, including As(III), As(V), and total inorganic arsenic, in drinking water. The technique combines ultraviolet-visible spectrophotometry with cloud point extraction (UV/CPE), ensuring high sensitivity and selectivity. The methodology relies on complex formation between As(III) and Pyronin B in the presence of tartaric acid. The resulting complex is efficiently extracted into the surfactant-rich phase consisting of 5.0% (v/v) Triton X-114. Under optimized conditions, a linear calibration relationship from 3 to 500 µg/L is obtained. The method offers low detection and quantification limits of 1.04 and 3.48 µg/L, respectively, with a corresponding relative standard deviation below 5% for 11 replicates. Furthermore, spiked samples demonstrated excellent recovery values from 95.1% to 102.3%. The accuracy was verified by the analysis of the standard reference material SRM 1643e (trace elements in water), revealing no significant differences at the 95% confidence level. The approach was successfully utilized for the quantification of As(III), As(V), and total inorganic arsenic in commercial and domestic drinking water.