The co-reduction of [Rh(C₂H₄)₂Cl]₂ and [Pd(η³-C₃H₅)Cl]₂ with vanadocene [Cp₂V] in THF, and in presence of poly(vinylpyrrolidone) (PVP), gives bimetallic PVP-protected Rh/Pd colloids. HREM and WAXS experiments show a narrow size distribution centered near 2 nm, indicating the existence of bimetallic particles rather than physical mixtures of monometallic ones. CO chemisorption, followed by IR in CH₂Cl₂, as well as catalytic hydrogenation of quinoline and phenylacetylene, followed by GC in CH₂Cl₂ or CH₂Cl₂/H₂O, confirm the presence of core/shell-structured bimetallic colloids, with Pd atoms surrounded by Rh atoms.