The polymer, polystyrene polydimethyl siloxane was loaded into the micropipette tip of the syringe system as an adsorbent to developed miniaturized solid phase microextraction. Standard solutions of arsenate and arsenite were passed through the adsorbent loaded in micropipette tip to check the adsorption behaviors. It was observed that arsenate adsorbed on the polystyrene polydimethyl siloxane in the pH rang of 6–8, while arsenite was directly passed through the micropipette tip of syringe system. The adsorbed arsenate in micropipette tip of syringe system were eluted by 1.0M hydrochloric acid. The total inorganic arsenic contents were obtained by the addition of oxidizing agent potassium permanganate into the studied samples before passing to the micropipette tip of syringe system. Arsenite concentration in water samples were measured by subtracting arsenate from total inorganic arsenic concentration. Different characteristics which effect the determination of arsenate specie like amount of adsorbent, adsorption capacity, pH, pulled and pushed cycles for adsorption and desorption, volume of sample, eluent type and it volume were also studied in detail. Enrichment factor and detection limit of arsenate by desired method were 218 and 6.9ngL−1 respectively. The relative standard deviation was 4.1% (n=10, C=0.12µgL−1). Accuracy of the desired technique was confirmed by analysis of the CRMs (Lake Ontario Water TM-28.3 and Riverine Water NRCC-SLRS-4). Desired technique was significantly useful for determination of the total arsenic, arsenate, and arsenite contents in different natural water samples. Display omitted •Miniaturized solid phase microextraction was developed by using micropipette tip of the syringe system.•Polystyrene polydimethyl siloxane was first time used as an adsorbent for inorganic arsenic specition and analysed by ET-AAS.•Simple, rapid, low cost and green extraction method was developed.•It was applied for determination of total As, arsenate and arsenite in real water samples from different location.•The aim of this work is to introduce an innovative green preconcentration approach.