The thermodynamic behavior and spin dynamics of the colossal magnetoresistive (CMR) perovskites of general formula La(1-x)(A)xMn(1-y)(B)yO3 (where A is an alkaline earth, and B = Al, In) have been studied in order to evidence the effect of composition and the influence of nanocrystallinity on the thermodynamic and magnetic characteristics. By using electron paramagnetic resonance (EPR) spectroscopy, the behavior of the exchange coupling integral (J) between Mn spins and the polaron activation energy (Ea) have been investigated. The thermodynamic properties represented by the relative partial molar free energies, enthalpies and entropies of oxygen dissolution in the perovskite phase, as well as the equilibrium partial pressures of oxygen have been obtained by using solid electrolyte electrochemical cells method. The influence of the oxygen stoichiometry change on the thermodynamic properties was examined using the data obtained by a coulometric titration technique coupled with measurements of the electromotive force (EMF). The results were correlated with the average Mn valence values as determined by redox titration. The properties of the rare-earth manganites are strongly affected by the A- and B-site substitution and by the oxygen nonstoichiometry. New features related to the modifications in properties connected with the nanocrystalline state were evidenced. The correlation existing between the magnetic and thermodynamic characteristics were discussed in relation to significant changes in the overall concentration of defects.