Plasma electrolytic oxidation (PEO) of an Al-Cu-Li alloy has been carried out with a pulsed-bipolar current regime in alkaline sodium aluminate electrolytes. Thick coatings can be developed under plasma discharges in electrolytes of 5 gl(-1) NaAlO2 + 1 gl(-1) KOH and 24 gl(-1) NaAlO2 + 1 gl(-1) KOH. In contrast, the alloy exhibits a conventional anodization behavior with the occurrence of galvanoluminescence in concentrated aluminate electrolyte of 32 gl(-1) NaAlO2 + 1 gl(-1) KOH, resulting in extremely thin nanoporous films and macropits on the alloy surface. It is proposed that, in the latter case, chemical attack from the electrolyte caused severer thinning of the original oxide film, paticularly at the weak sites of anodic constituent particles or precipitates, which then triggers strong field-assisted dissolution of the oxide film, preventing the further growth of the coating. However, after the formation of a thin pre-existing film(similar to 1-2 mu m) on the alloy in less concentrated electrolytes, then thick coatings develop more rapidly in 32 gl(-1) NaAlO2 + 1 gl(-1) KOH, since the field-assisted dissolution is only prevalent in extremely thin films and retreats quickly as the film thickens. Long-term immersion in aluminate electrolytes can eliminate all the weak points on the alloy surface and the oxide film is repaired, thus thicker PEO coatings can also be developed in concentrated electrolytes. (C) 2014 Elsevier Ltd. All rights reserved.