Embedding　a　functional　metal-oxo　cluster　within　the　matrix　of　metal-organic　frameworks　(MOFs)　is　a　feasible　approach　for　the　development　of　advanced　porous　materials.　Herein,　three　isoreticular　pillar-layered　MOFs　(Co-6-MOF-1-3)　based　on　a　unique　[Co-6(mu(3)-OH)(6)]　cluster　were　designed,　synthesized,　and　structurally　characterized.　For　these　Co-6-MOFs,　tuning　of　the　framework　backbone　was　facilitated　due　to　the　existence　of　second　ligands,　which　results　in　adjustable　apertures　(8.8　to　13.4　angstrom)　and　high　Brunauer-EmmettTeller　surfaces　(1896　2401　m(2)　g(-1)).　As　the　[Co-6(mu(3)-OH)(6)]　cluster　has　variable　valences,　these　MOFs　were　then　utilized　as　heterogeneous　catalysts　for　the　selective　oxidation　of　styrene　and　benzyl　alcohol,　showing　high　conversion　(＞90%)　and　good　selectivity.　The　selectivity　of　styrene　to　styrene　oxide　surpassed　80%　and　that　of　benzyl　alcohol　to　benzaldehyde　was　up　to　98%.　The　calculated　TOF　values　show　that　the　increase　of　reaction　rate　is　positively　correlated　with　the　enlargement　of　pore　sizes　in　these　MOFs.　Further,　a　stability　test　and　cycling　experiment　proved　that　these　Co-6-MOFs　have　well-　observed　stability　and　recyclability.