The X-ray structural analyses of homoleptic Rh(II) complexes made of enantiopure (R)-1,1′-binaphthyl and (R)-(5,5′,6,6′,7,7′,8,8′-octahydro)binaphthyl phosphate ligands are for the first time presented. The possibility to introduce halogen atoms at the 3,3′-positions is also reported. The isolated dirhodium complexes were further tested as catalysts (1 mol %) in enantioselective cyclopropanations and Si–H insertion reactions, affording chiral cyclopropanes and silanes in good yield but moderate enantioselectivity (ee max 63%).