A novel in-line anion exchange separation method is described for the removal of Mn2+, Fe3+, Ni2+, Co2+, Cu2+, Zn2+, and Pb2+ from Cd2+ and for its subsequent determination by vapor generation atomic absorption spectrometry. High Cd2+ retention efficiency and maximum exclusion of other metal ions were achieved by using Cl-, Br-, or I- loaded strong base anion exchange resin and fiber in chloride medium. SO4 2- and NO3 - affected the retention of Cd2+ on Cl- or Br- loaded exchangers but were beneficial for elution from I- loaded exchangers. Fast and efficient elution from the exchangers was achieved by using ethylenediamine solution. The removal of Zn2+ was unnecessary as it prevents a decline in the sensitivity of cadmium response when ethylenediamine and high acid concentration were used. Under optimum conditions, the achievable detection limits (3σ) with sample loadings of 0.48 and 9.6 mL were 40 ng L-1 and 3 ng L-1, respectively. Interference of residual organic matrix, in sample digests, with the separation and retention of cadmium were eliminated by use of microwave assisted digestion. The method was successfully applied to the determination of Cd in river sediment, fish liver, and water samples.