Synthesis and application of a task-specific ionic liquids (TSILs) as extracting solvents or chelating agents in dispersive liquid–liquid micro-extraction (DLLME) was evaluated. The developed method was based on the use of an ammonium pyrrolidine dithiocarbamate (APDC) bonded ionic liquid for chelation with As(III), followed by conversion of the As(III) chelated TSIL to a hydrophobic ionic liquid using KPF₆ as an anion-exchange reagent. As(V) was reduced to As(III), using a 2/1 w/w blend of KI and Na₂S₂O₃ and then the total amount of As was measured through ETAAS analysis. Under optimal conditions, linear dynamic ranges of 0.2–15 ng mL⁻¹ and 0.2–20 ng mL⁻¹ were observed in the determination of As(III) and total As respectively. The relative standard deviations (RSD%, n = 5) for the determination of As(III) (10 ng mL⁻¹) was 3.2% and the limits of detection and quantitation were determined to be 0.01 ng mL⁻¹ and 0.0.034 ng mL⁻¹; respectively.