Natural phosphates are an important natural resource in Morocco, which needs to be valorised. They can be used not only as fertilisers but also as catalysts. Here, we report for the first time on its use as support for platinum and the application of the resulting systems to the liquid-phase selective hydrogenation of an α,β-unsaturated carbonyl compound (crotonaldehyde) to the corresponding unsaturated alcohol (crotyl alcohol), a process of interest in the production of pharmaceuticals, agrochemicals and fragrances. Catalytic results are related to the surface solid structure as determined by XPS. Therefore, the most active systems showed new surface interactions as evidenced by the appearance of new P, O, Ca, F and C peaks and the shift of Pt ones to lower binding energies. Further modification of the most active system with FeCl(2) led to 70% selectivity to crotyl alcohol at 34% conversion.