Attempt has been made to obtain the relationship between the electrophysical and electrochemical properties in order to provide a possible basis for designing new electrode materials for fuel cell applications. The substituted lanthanum cuprates of composition La2-xMxCu1-yM'O-y(4) (where M = Sr, Ca and Ba; M' = Sb and Ru; 0.0 less than or equal to x less than or equal to 0.4 and y = 0.1) were used to demonstrate the correlation of the Fermi level and carrier concentration with the methanol oxidation onset potential and activity, respectively. The activity of bulk material is compared with that of the nanocrystalline material prepared by the polymer modified sol-gel method. The nanocrystalline material was characterized by TGA, XRD, SEM, TEM and cyclic voltammetry. (C) 2002 Published by Elsevier Science Ltd.