The effect of the P/Rh ratio and the surfactant concentration on the partial hydrogenation of sunflower oil in Triton X-100 microemulsion systems with the water-soluble catalyst complex Rh-TPPTS has been studied. An unusual hindering effect of the surfactant on the production of elaidic acid and stearic acid as the oil is hydrogenated was observed. When increasing the concentration of Triton X-100 in the reaction medium from 3 to 15 wt%, the content of elaidic acid and stearic acid were lowered 21 and 34%, respectively. The maximum content of oleic acid was attained when the concentration of Triton X-100 was 15 wt%, obtaining a high content of 51.8% of oleic acid. When the ligand/metal ratio was higher, the reaction was slower but more selective to oleic acid. The Rh-TPPTS catalyst could be recycled up to 3 times after hydrogenation of sunflower oil by extracting the oil phase of a three-phase microemulsion system, observing a continuous deactivation of the catalyst.