A simple analytical procedure is proposed for simultaneous determination of three common dyes (Basic Blue 9, Brilliant Blue E-4BA, and Reactive Blue 2) in natural waters without prior separation of the solutes. A popular chemometric method, partial least squares regression PLS-1, was effectively applied for spectral resolution of a highly overlapping system. At the best modeling conditions, mean recoveries and relative standard deviations (RSD) for dyes quantification by PLS-1 were found to be 102.1 (4.4), 95.7 (8.4), and 98.9 (6.2) for Basic Blue, Brilliant Blue, and Reactive Blue, respectively. The estimated limits of detection (LOD) were estimated using net-analyte signal concept and were 0.11, 0.52, 0.49mg L-1 for Basic Blue, Brilliant Blue, and Reactive Blue, respectively. The quantitative determination of dyes spiked in real water samples was carried out successfully by PLS-1 with satisfactory recoveries for dyes (90-106%). [ABSTRACT FROM AUTHOR]