Among the large class of Heusler compounds. Co2CrAl is predicted to be 100% spin polarized and is hence, a potential candidate for application in spintronics. So far, the predicted properties have not been experimentally realized which may be attributed to the phase segregated nature of samples. This phase segregation is avoided using floating zone growth. However, the grown sample was found to have undergone phase transformation via spinodal decomposition at low temperatures. In the present work, thermal annealing has been done on the spinodally decomposed samples and its effect on microstructure, crystallographic structure and magnetic properties has been studied. Annealing experiments were done and analyzed in order to understand the extent of the solid state miscibility gap. With regards to the phase diagram, the two-phase regime was found to extend till 1000 degrees C. Even at 1250 degrees C, we are still inside the immiscibility region. The thermodynamic miscibility gap was thus found to exist until high temperatures and alternate routes might be required to obtain a single phase sample with the desired high spin polarization and Curie temperature in the Co-Cr-Al system. (C) 2014 Elsevier By. All rights reserved.