The insertion of an excess of oxygen within the structure of La2-xCaxCuO4 (x less than or equal to 0.12) by means of room temperature chemical oxidation modifies the physical properties and the crystal structure of these cuprates. The superconducting features of the starting La2-xCaxCuO4 samples improve considerably upon oxidation. The oxidized Ca-doped materials with x less than or equal to 0.08 show an almost constant T-c of similar to 38 K, close to that corresponding to the optimum hole-doping in La2-xMxCuO4; however, the oxidized samples with higher Ca contents present slightly lower T(c)s. This decrease of T-c is connected with the ability of these compounds to incorporate extra oxygen, which decreases as the Ca-doping increases and is controlled by a structural limit. The behavior of the La2-xCaxCuO4 materials under the oxidation process and the changes induced by the interstitial oxygen are strongly conditioned by the smaller size of Ca2+ with respect to La3+. Indeed, this peculiarity clearly differentiates the oxidized La2-xCaxCuO4+y series from the Sr2+ and the Ba2+ substituted systems, where the size of the dopant is larger than that of La3+. In the present work the analogies and the differences concerning the insertion of oxygen and the modifications induced in La2-xMxCuO4+y (M = Ca, Sr, Ba) are presented and discussed. (C) 1998 Elsevier Science B.V.