The　selective　oxidation　of　methane　(CH4)　has　attractive　potentials　for　mitigating　global　warming　and　producing　value-added　chemicals,　whereas　the　efficient　generation　of　multicarbon　products　such　as　ethanol　remains　challenging,　due　to　the　short　lifetimes　and　high　unpaired　concentrations　of　reactive　intermediates　(like　center　dot　OH,　center　dot　CH3,　center　dot　OCH3,　and　center　dot　CH2OH).　Herein,　we　developed　a　medium-spin　Zn-O-Fe(MS)　catalyst　with　tunable　Fe(III)　spin　states,　which　can　efficiently　photo-oxidize　CH4　to　ethanol　at　ambient　conditions.　The　unpaired　electrons　in　d　orbitals　of　Fe　sites　allow　for　efficient　adsorption　of　center　dot　OH,　and　the　e(g)　orbital　occupancy　enables　stabilizing　different　key　carbon-containing　intermediates　(center　dot　OCH3　versus　center　dot　CH2OH).　By　balancing　those　two　descriptors,　the　medium-spin　Zn-O-Fe(MS)　catalyst　allows　to　achieve　selective　generation　of　center　dot　CH2OH　intermediates　with　a　moderate　*OH　coverage　and　subsequent　coupling　of　center　dot　CH3　and　center　dot　CH2OH　to　ethanol.　With　a　light　intensity　of　100　mWcm(-2)　and　water　as　a　weak　oxidant,　the　Zn-O-Fe(MS)　catalyst　exhibited　a　peak　photocatalytic　CH4-to-ethanol　yield　of　372　mu　molg(-1)h(-1)　without　the　use　of　photosensitizers　or　sacrificial　reagents,　which　is　similar　to　3　times　higher　than　the　previously　best　reported　photocatalytic　CH4　oxidation　to　ethanol　under　similar　conditions.　Our　study　suggests　an　attractive　potential　of　converting　CH4　to　multicarbon　products　by　modulating　spin　states　of　the　catalytic　sites.