The two reactions between iron ion (Fe3+ ) and o-chlorophenylfluorone (o-CPF) and copper ion (Cu2+ ) and o-CPF are sensitive at pH 6 in the presence of Triton X-100. We have determined the formation constants of the complexes by the spectral correction technique. Because of the poor selectivity of o-CPF to metals, the competition coordination of only the iron ion from the Cu-o-CPF complex was found and applied to the selective detection of iron traces by the Selective Competition Coordination Determination (SCCD) approach.The analysis of several samples shows that the relative standard deviations are less than 5.0% and the recovery of iron ions between 94.5% and 106%.