We developed a cost-effective and sensitive spectrophotometric method for the determination of arsenic at trace level using a new reagent, leuco malachite green. Here we show that, arsenic reacts with potassium iodate in acidic conditions to liberate iodine, and the liberated iodine selectively oxidizes leuco malachite green to malachite green dye. We studied the Beer’s law at 617 nm, which showed linearity over the concentration range 0.09–0.9 μg ml−1 of arsenic. We show that the molar absorptivity, Sandell’s sensitivity and detection limit of the method are 6.1 × 104 l mol−1 cm−1, 0.0012 μg cm−2 and 0.025 μg ml−1, respectively. We applied the developed method for the determination of arsenic in environmental samples.