A new spectrophotometric method for mercury determination has been developed based on the complexation of mercury(II) in ascertained excess of thiocyanate. The remaining thiocyanate is reacted with iron(III) to form a red iron(III)-thiocyanate complex which gave maximum absorbance at 460 nm. The concentration of mercury(II) is inversely proportional to the decrease absorbance of the complex. The method was optimized to the concentrations of thiocyanate and iron(III). Selectivity of the method has also studied based on percent recovery of mercury(II) in the presence of common metal ions in the tailing waters of gold mine. Under the optimum conditions, the method showed linear correlation to mercury(II) concentration from 1-30 mg L−1 with detection limit of 0.58 mg L−1. The method was not interfered in the presence of all metal ions studied up to 50 mg L−1, except of silver which was tolerated at 10 mg L−1. The developed method has been satisfactorily applied for mercury(II) determination in synthetic and tailing waters of gold mine samples.