The influence of the Co addition and synthesis route on desorption properties of MgH2 were investigated. Ball milling of MgH2-Co blends was performed under Ar using different milling intensities and different weight ratios. Microstructural and morphological characterization, performed by XRD and SEM, show a huge correlation with thermal stability and hydrogen desorption properties investigated by DSC. A complex desorption behaviour is correlated with the dispersion of the catalytic particles that appears to play a main role in desorption performances. The optimum catalyst concentration was found to be around 10 wt.%, while the optimum value of the ball to powder ratio was 10:1.