A solid phase preconcentration procedure using hybrid sorbent based on nano zirconium dioxide-boron oxide for the speciation and determination of As(III), As(V) and total As in water samples by hydride generation atomic absorption spectrometry (HGAAS) was presented. Experimental parameters including pH, sample volume, flow rate, volume and concentration of eluent that affect the recovery of the arsenic species have been optimized. Under optimized experimental conditions, analytical parameters including limit of detection, limit of quantification, linear working range, precision and accuracy have also been determined. Interfering effects of matrix constituent on the recovery of the arsenic were studied. The reusability and adsorption capacity of the new hybrid sorbent were also investigated. The hybrid sorbent was successfully applied for preconcentration and speciation of arsenic(V) from various samples with recovery of 99 +/- 5%. The analytical limit of detection was found 9.25 ng/L The hybrid sorbent was stable up to 100 runs. Adsorption capacities of the hybrid sorbent were 98.04 mg/g for As(V). The accuracy of the method was tested by analyzing certified reference material (SPS-WW1 Waste Water) and spiked real samples. The method has been applied for the determination of analytes in tap water, underground water. (C) 2011 Elsevier B.V. All rights reserved.