For La1-2xNaxKxMnO3+5-type samples, the structural defects and their evolution vs. La-substituents were investigated. Models for the structural defects were determined based on the compositional dependence of the average oxidation state of manganese ions in air synthesized samples (quenched from 800 degreesC), the sample lattice parameters, and pycnometrically determined sample densities. (C) 2003 Elsevier Science B.V. All rights reserved.