A noble method for pre-concentration and speciation of ultra trace As (III) and As (V) in urine and whole blood samples based on dispersive liquid-liquid microextraction (DLLME) has been developed. In this method, As (III) was complexed with ammonium pyrrolidine dithiocarbamate at pH = 4 and Then, As (III) was extracted into the ionic liquid (IL). Finally, As (III) was back-extracted from the IL with hydrochloric acid (HCl) and its concentration was determined by flow injection coupled with hydride generation atomic absorption spectrometry (FI-HGAAS). Total amount of arsenic was determined by reducing As (V) to As (III) with potassium iodide (KI) and ascorbic acid in HCl solution and then, As (V) was calculated by the subtracting the total arsenic and As (III) content. Under the optimum conditions, for 5-15 mL of blood and urine samples, the detection limit ($3{sigma}$) and linear range were achieved 5 ng $L^{-1}$ and 0.02-10 ${mu}g;L^{-1}$, respectively. The method was applied successfully to the speciation and determination of As (III) and As (V) in biological samples of multiple sclerosis patients with suitable precision results (RSD < 5%). Validation of the methodology was performed by the standard reference material (CRM).