The ionic transport properties of alkaline polymer electrolytes based on poly(vinyl) alcohol (PVA) have systematically been studied using a Hittorf's method. The ionic transport numbers for three types of alkaline PVA-based polymer electrolytes, including PVA, PVA/PECH blend, PVA/TEAC blend, were measured in this work. It was found that the anionic transport number (t(-)) was in the range of between 0.82 and 0.99; it strongly depends on the types of alkali metal salts, and the chemical compositions of polymer electrolytes. However, it only slightly depends on the applied current densities. Experimental results indicated that alkaline PVA/TEAC blend polymer electrolytes showed the highest value of anionic transport number, as compared with PVA and PVA/PECH blend polymer electrolytes. (c) 2005 Elsevier B.V. All rights reserved.