In this work, the phase diagram of poly(3-hexyl thiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) blends is measured by means of standard and modulated temperature differential scanning calorimetry. Blends were made by solvent-casting from chlorobenzene, as blends cast from toluene or 1,2-dichlorobenzene prove to retain effects of phase segregation during casting, hindering the determination of the phase diagram. The film morphology of P3HT/PCBM blends cast from chlorobenzene results from a dual crystallization behavior, in which the crystallization of each component is hindered by the other component. A single glass transition is observed for all compositions. The glass transition temperature (Tg) increases with increasing concentration of PCBM: from 12.1 degrees C for pure P3HT to 131.2 degrees C for pure PCBM. The observed Tg defines the operating window for the thermal annealing and explains the long-term instability of both the morphology and the photovoltaic performance of the P3HT/PCBM solar cells.