An ion exchange procedure was developed for the enrichment, separation and quantification of butyltin and phenyltin species, which show very close half wave potentials by their voltammetric determination. As a case study the separation of dibutyltin (DBT) from triphenyltin (TPT) was investigated. Among different ion exchangers tested, the strong acid ion exchanger PUROLITE C100H, used for industrial purposes, was found to be the most suitable. By using a resin bed volume of 25 mL, a flow rate of the feed solution of 1 mL/min and 3 M HCl in methanol as eluent with a flow rate of 0.5 mL/min, a recovery rate of each species of about 80% could be achieved. The detection limit for the determination of DBT and TPT by anodic stripping voltammetry after their separation and enrichment by the above mentioned ion exchange procedure was found to be 0.4 ng/mL for DBT and 6 ng/mL for TPT in the feed solution, respectively. The applicability of the whole procedure was tested on a sediment candidate reference material of BCR (Bureau of Reference Community).