A newly analytical method has been developed to determine total chromium and speciation of this element in water samples through dispersive liquid-liquid microextraction combined with a high-resolution continuum source flame atomic absorption spectrometry. The most significant variables affecting complexation and extraction were optimized by using response surface methodology and univariate optimization. The best conditions for both the complexation and extraction elements in this study were: complexing agent ammonium pyrrolidine dithiocarbamate (APDC 6.0 mmol L ) and 19 for total Cr. The method accuracy was carried out by using certified water reference material (NIST CRM 1643e), and the results achieved were in agreement with the certified value (t-test at a confidence interval of 95%). The method developed was applied in samples of mineral water, tap water (the recovery values ranged from 88 to 115%) and seawater.