The changes introduced by both ball milling and the addition of small amounts of TiF3 in the kinetics of the hydrogen desorption of three different Ca(BH4)2 polymorphs (α, β and γ) have been systematically investigated. The samples with different polymorphic contents, before and after the addition of TiF3, were characterized by powder X-ray diffraction and vibrational spectroscopy. The hydrogen desorption reaction pathways were monitored by differential scanning calorimetry. The hydrogen desorption of Ca(BH4)2 depends strongly on the amount of coexistent α, β and γ polymorphs as well as additional ball milling and added TiF3 to the sample. The addition of TiF3 increased the hydrogen desorption rate without significant dissociation of the fluoride. The combination of an α-Ca(BH4)2 rich sample with 10 mol% of TiF3 and 8 h of milling led to up to 27 ∘C decrease of the hydrogen desorption peak temperature.