AbstractRhodium precursor catalysts supported on palygorskite, montmorillonite and silica were obtained from an organometallic cationic rhodium species and evacuated supports at different temperatures. Based on the different times which precursors took to be active in 1‐hexene hydrogenation, in the liquid phase at atmospheric hydrogen pressure, it has been deduced that the supported rhodium species varies with the support and its dehydration temperature. Activity in this reaction also depended on the support, its dehydration temperature and storage in air. Precursors and catalysts were characterized by X‐ray photoelectron and infrared spectroscopy. Very stable complexes are obtained under humid ambient conditions. With montmorillonite support, activity decreases if rhodium/1‐hexene ratio decreases.