A certified reference material (NIST-RM-50 Albacore Tuna) was analysed for selenium by cathodic stripping voltammetry (CSV), after digestion of the material by a number of methods that avoid the use of perchloric acid. The digestion techniques tested included wet and dry ashing methods, oxygen bomb digestion, ultraviolet (UV) digestion, and methods involving elevated pressure. The only method that reliably produced results that agreed with the certified value for selenium in the reference material was the combination wet/dry ashing method incorporating elevated pressure recommended by the Association of Official Analytical Chemists (AOAC) for determination using hydride generation atomic absorption spectrometry (AAS). Recoveries using the other methods were low and variable, apparently because of incomplete destruction of organic matter and losses caused by volatilisation of selenium.