A new rapid, selective and sensitive on-line microwave flow injection-kinetic method was developed for spectrophotometric determination of micro amounts of Ir(III), based on its catalytic effect on the m-acetylchlorophosphonazo (CPA-mA) and KIO(4) reaction in NaOH media. An on-line microwave oven was employed to accelerate the reaction. The reaction was followed spectrophotometrically by measuring the decrease of the absorbance of CPA-mA at 580 nm. The effect of five variables for the determination of Ir(III) was optimized by means of a multilayer artificial neural network using extended delta-bar-delta (EDBD) algorithms. Under the optimum experimental conditions, Ir(III) could be determined in the range 0.060-0.60 micro gZZZ;mL(-1) with detection limit of 0.02 micro gZZZ;mL(-1) and the sampling frequency of 34 h(-1). The proposed method was applied to the determination of micro amounts of Ir(III) in refined ore and secondary alloy with the recoveries from 91.4% to 109%.