An analytical methodology was developed for the first time in this work enabling the simultaneous enantiomeric separation of the fungicide fenpropidin and its acid metabolite by Capillary Electrophoresis. A dual cyclodextrin system consisting of 4 % (w/v) captisol with 10 mM methyl-beta-cyclodextrin was employed in a 100 mM sodium acetate buffer at pH 4.0. Optimal experimental conditions (temperature 25 degrees C, separation voltage -25 kV, and hydrodynamic injection of 50 mbar x 10 s) allowed the simultaneous separation of the four enantiomers in <10.7 min with resolutions of 3.1 (fenpropidin) and 3.2 (its acid metabolite). Analytical characteristics of the method were evaluated and found adequate for the quantification of both chiral compounds with a linearity range from 0.75 to 70 mg L-1, good accuracy (trueness included 100 % recovery, precision with RSD<6 %), and limits of detection and quantification of 0.25 and 0.75 mg L-1, respectively, for the four enantiomers. No significant differences were found between the concentrations determined and labelled of fenpropidin in a commercial agrochemical formulation. The stability over time (0-42 days) of fenpropidin enantiomers using the commercial agrochemical formulation was evaluated in two sugar beet soils, revealing to be stable at any time in one sample, while in the other a decrease of 45 % was observed after 42 days. Individual and combined toxicity of fenpropidin and its metabolite was determined for the first time for marine organism Vibrio fischeri, demonstrating higher damage caused by parent compound. Synergistics and antagonists' interactions were observed at low and high effects levels of contaminants.