An ion exchange methodology is described here for the quantitative separation and determination of trace elements from high purity gallium, arsenic and a mixture of gallium and arsenic. 0.5-2g of the matrix is dissolved and subjected to an ion exchange separation process in acidic/alkaline (hydrochloric acid/ammonia with sodium hydroxide) medium to preconcentrate the analytes. The desorbed analytes were quantified using graphite furnace atomic absorption spectrometry/flame atomic absorption spectrometry/flame atomic emission spectrometry/neutron activation analysis/inductively coupled plasma atomic emission spectrometry. Most of the analytes were found to be present at extreme trace levels. The overall reproducibility of the procedure was 2-10% when compared with the blank values. Separation of the analytes were essentially complete as the recoveries were >95% which was confirmed by standard addition to the matrices and tracer studies.