Calcium-substituted lanthanum manganites La1-xCaxMnO3+delta (0 less than or equal to x less than or equal to 1) were synthesized from the solid oxide precursors using two routes: a traditional ceramic method and the mechanical activation of the mixture of oxides in high power planetary ball mills, followed by the product annealing at different temperatures. The samples structure was studied by XPD and TEM methods, while their surface composition was characterized by the differential dissolution method. A pronounced effect of the preparation method on samples bulk and surface properties, reflected in their reactivity characterized by the rare of CO catalytic oxidation, was observed. For samples prepared via the ceramic route by sintering at 1100 degreesC, continuous solid solutions are formed. In the case of mechanical activation route, by annealing of activated mixture of oxides at 700-100 degreesC, solid solutions are formed only at the Ca content within 0 less than or equal to x less than or equal to 0.4 range. At higher Ca content, microheterogeneous composites are formed, in which the nucleus of particles is formed by the perovskite phase with x less than or equal to 0.4, while the surface layer is enriched by Ca. The catalytic activity in CO oxidation appears to correlate with the density of extended defects, being decreased when Ca is segregated in the surface layer,