A dual-layer ion-exchange latex-coated column was prepared and characterised for on-capillary preconcentration of cations using an open-tubular ion-exchange CEC format. After preconcentration, the analyte cations were eluted with a transient isotachophoretic gradient and separated by CE. The latex double layer was established by first coating the negatively charged wall of the capillary with a layer of cationic quaternary ammonium anion-exchange Dionex AS5A latex particles (60 nm diameter), and then coating a layer of anionic sulphonated cation-exchange Dionex CS3 latex particles (300 nm diameter) onto the underlying AS5A layer. The adhesion of layers is based on electrostatic attractions. Several dual-layer capillaries were characterised for their EOF and ion-exchange capacity and this showed that coatings could be prepared reproducibly by a simple flushing procedure. The dual-layer columns exhibited a moderate, pH-independent EOF (ca. 26 x 10(-9) m(2) V-1 s(-1)) and an ion-exchange capacity of 57 mu equiv./g (or 2.69 nequiv./column). Using an 8 cm length of coated capillary combined with a 72 cm length of untreated capillary, a method for on-line preconcentration and separation of monovalent organic bases, alkali metal ions and alkaline earth metal ions by CE was developed. Recoveries for the preconcentration step were 48% for 4-methylbenzylammonium, 43% for benzylammonium, 30-32% for alkali metal ions and 71-75% for alkaline earth cations. In all cases, recoveries were reproducible with RSDs being less than 6.2%. The influences of the ion-exchange selectivity coefficient of the analyte and the sample-loading rate on analyte recovery were also examined. The proposed method was utilised for the determination of alkaline earth cations and low mu M detection limits were obtained.