Cationic‐shell core‐crosslinked micelles (CCM‐C) with rhodium nanoparticles (RhNPs) anchored to core‐linked triphenylphosphine oxide (TPPO) ligands were synthesized by a facile one‐pot approach by the reduction of [Rh(COD)(µ‐Cl)]2/toluene in the presence of an aqueous TPPO@CCM‐C latex. The resulting RhNP‐TPPO@CCM‐C latex showed to be performant for the aqueous biphasic hydrogenation of styrene with an average corrected turnover frequency (cTOF) up to 23600 h‐1 based on the RhNP surface atoms. The catalyst system also proved reusable in multiple catalytic runs without any visible RhNP loss during the recycling process as well as applicable to the hydrogenation of other selected alkenes, alkynes and carbonyl substrates (average cTOF of 1000–3200 h‐1), thus demonstrating a high versatility.