The phosphane-hydroxyl ligand (S C1 ,R C2 )-Ph 2 PC(Ph)HC-(OH)HCH 2 OMe (POH) displays κ 1 P, κ 2 P,O, κ 3 P,O,O′, and anionic deprotonated κ 3 P,O,O′ coordination modes toward the metallic (η 6 -pMeC 6 H 4 iPr)Ru moiety. The hydroxyl group in [(η 6 -p-MeC 6 H 4 iPr)Ru-(κ 3 P,O,O′-POH)][SbF 6 ] 2 (3) has strong acidic properties. This complex catalyzes the Diels−Alder reaction between cyclopentadiene and trans-β-nitrostyrene or methacrolein as well as the Friedel−Crafts reaction between indole and methyl 3,3,3,-trifluoropyruvate or trans-β-nitrostyrene. Solution studies strongly indicate that complex 3 acts as a metallic Lewis acid assisted Brønsted-acid catalyst.