The evolution of structural-morphological characteristics of ZnO + 1 wt.% MnO2 and ZnO + 10 wt.% MnO2 samples during prolonged mechanical treatment (MT) was investigated by X-ray, AFM, LPS, SEM and IR methods. Changes in crystallite size due to mechanical activation were determined from X-ray measurements. These results were correlated with changes in particle size followed by SEM and AFM. Particle and aggregate size distributions were determined from LPS measurements. Interpretation of the evolution of IR-absorption peaks during mechanical activation using the theory of average dielectric constants enabled analysis of changes of particle and agglomerate shapes. All these results enabled establishment of a relationship between crystallites, particles, aggregates of particles, and superficial processes that occur during mechanical activation. (C) 2009 Elsevier B.V. All rights reserved.