This paper describes the application of the well-known Molybdenum Blue method for selective determination of arsenite in a flow injection system. Selectivity is achieved by on-line separation of the main interferents phosphate, arsenate and silicate using a strong anion-exchange microcolumn located in the aspiration line of injection valve. Arsenite passing through the microcolumn unretained is determined using Molybdenum Blue method following on-line oxidation to arsenate by permanganate. A thorough investigation of optimal experimental conditions for both, the separation of interferents and sensitive detection of arsenite is presented. The method developed permits arsenite to be determined in the concentration range 5-500 mu g/l with high precision and reliability. A sample throughput of 20 hr(-1) is achieved. Phosphate, arsenate and silicate do not interfere at concentration levels significantly higher than that of arsenite. The application to real water samples reveals excellent recovery of spiked samples and the absence of matrix interferences.