The separation and detection of inorganic ions on microfluidic devices has received little attention since the 'lab-on-a-chip' concept has revolutionised the field of electrokinetically driven analysis. This review presents a summary and discussion of the published literature on inorganic analysis using microfluidic devices and includes sections on electromigration separation methods, namely isotachophoresis (ITP), capillary electrophoresis (CE), and hyphenated ITP-CE, together with a brief account of flow injection analysis. The review concludes with the authors' perspective on future directions for inorganic analysis on microfluidic devices.