In this study, the speciation of iron (Fe), including total Fe (TFe) and acidified dissolved Fe (ADFe), was assessed by fast cathodic absorption stripping voltammetry, using a gold electrode and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) as a novel complexing agent for Fe. The validity and accuracy of this method were compared with the standard spectrophotometry and tested by the standard samples. Under optimized conditions, the Fe response was linear within the range of 0.01 to 1 μM with a detection limit of 1.2 nM. To further validate this method, the variation in concentrations of TFe and ADFe were investigated at twelve sampling stations in a local coastal river, in both the dry and wet season. Additionally, to further understand the interaction between Fe and environmental factors, the relationships between the concentration of Fe species and dissolved oxygen (DO) and salinity were also discussed.