A simple and efficient electrochemical assay based on self-assembled monolayers (SAMs) was developed for the highly sensitive determination of arsenic(III) in water samples. The synergy of glutathione (GSH), dithiothreitol (DTT) and N-acetyl-L-cysteine (NAC) mixed SAMs enhanced the detection specificity and sensitivity of As(III) in water samples, resulting from the immobilization of a large number of As(III) moieties on the gold electrode surface via As-O and As-S linkages. After accumulating As(III), anodic stripping voltammetry (ASV) was performed, and linear sweep voltammetry (LSV) was employed for signal recording. Several main voltammetric parameters were optimized as follows: supporting electrolyte, 1 mol L À1 HCl; deposition potential, À0.35 V; deposition time, 150 s. A good linear relationship (R ¼ 0.9980) was attained between the concentration of the As(III) standard and peak current, in the range of 3-100 mg L
À1. The limit of detection (LOD) of this sensing system was determined to be 0.5 mg L À1 at a signal-to-noise ratio of 3. A variety of common coexistent ions in water samples were examined, showing no obvious interferences on the As(III) determination. The amenability of this method to the analyses of water samples was also investigated. High recovery of 90.5% with the precision of 5.1% at spiked 10 mg L À1 , and low LOD of 0.3 mg L À1 were obtained in seawater. The synergy effect of GSH, DTT and NAC provided the possibility for the rapid and sensitive LSV determination of As(III) in complicated water samples.