A theoretical analysis of chlorophyll a (Chla) hydration processes in aqueous Organic Solvents has been carried Out by means Of quantum chemistry calculations. A detailed knowledge of the thermodynamics of these processes is fundamental in order to better Understand the organization of chlorophyll molecules ill vivo, specifically the Structure of chlorophyll pairs in photosystems I and II. III the present work, we assumed a Chla model in which the phytyl chain is replaced by a methyl group. Calculations were performed at the B3LYP/6-31G(d) level corrected for basis Set superposition errors and dispersion interaction energy. This computational scheme was previously Shown to provide data close to MP2/6-311++(2d,2p) results. Solvents effects were taken into account Using either Continuum (for nonpolar solvents) or discrete-continuum (for polar coordinating solvents) methods. III the latter case, we first examined the Structure of Chla in rigorously dry Solutions. Two types of solvents were Characterized according to Mg-atom coordination: In type I solvents (acetone, acetonitrile, DMSO), Mg exhibits five-coordination, whereas in type II solvents (THF, pyridine), Mg exhibits six-coordination. Hydration processes are quite dependent oil solvent nature. In nonpolar or low-polarity solvents such as cyclohexane or chloroform, hydration is always exothermic and exergonic, despite a large entropy term that strongly opposes hydration. III polar solvents of type 11, hydration is quite unfavorable, and essentially no hydrates are expected in these media, except perhaps at very large water concentrations (although, ill Such a case, the medium cannot be simply described as an organic solvent). Ill polar solvents of type 1, the Situation is intermediate, and dihydration is favorable in some cases (acetone, acetonitrile) and unfavorable in others (DMSO). It is interesting to note that first hydration processes in coordinating solvents (of either type I or type II), where a Water Molecule Must displace I solvent molecule coordinated to Mg, exhibit values of Delta H > 0 and Delta S > 0, in sharp contrast to first hydration processes in nonpolar media. The present results represent the first theoretical attempt to rationalize the large amount of experimental data on hydration and aggregation of Chla in aqueous Organic media that have been accumulated over the past four decades. The data stress, in particular, the key role of Chla dihydrates, a point that has been the object of intense debate in the literature. Clearly, dihydrates are found to be more stable than monohydrates owing to a particular Structure ill which cooperative interactions occur between the water molecules and Chla. The Calculations also explain the irregular behavior observed for Chla in aqueous THF or pyridine: III these media, Chla remains basically unhydrated because the Chla-solvent adducts are stabilized by strong dispersion interactions.