CH3OH　is　the　most　desired　product　of　photocatalytic　CH4　conversion.　The　prominent　metal-decorated　photocatalyst　is　challenging　in　both　high　yield　and　selectivity　for　CH3OH　products　due　to　over-oxidation　by　center　dot　OH　mechanism.　Here,　interstitial　Zn　is　fabricated　into　ZniO　to　induce　the　formation　of　Zn　atom　island　for　rapid　single　electron　reduction　of　O2　into　center　dot　OOH　instead　of　center　dot　OH　for　the　selective　combination　with　methyl　into　CH3OOH.　AuPd　alloy　is　simultaneously　decorated　on　ZniO　surface　for　tuning　CH3OOH　adsorption　and　reduction　into　CH3OH.　The　synergy　of　Zn　atom　island　and　AuPd　alloy　achieve　a　tandem　reaction　pathway　(CH4　-＞　CH3OOH　-＞　CH3OH)　for　an　unprecedented　CH3OH　yield　of　2444　mmol　gAuPd-1　h-1　(or　8800　mu　mol　gcat-1　h-1)　with　98.3%　selectivity,　which　bypasses　the　center　dot　OH　mechanism　for　tuning　the　high　selectivity　of　CH3OH.　An　apparent　quantum　efficiency　of　18.53%　at　370　nm　for　CH4　conversion　are　super　to　the　reported　photocatalytic　systems.　Thus,　this　work　provides　the　new　strategy　of　the　synergetic　atom　island　and　metal　alloy　photocatalysts　through　a　tandem　reaction　pathway　to　mediate　the　photocatalytic　selective　oxidation　of　CH4　into　the　desired　CH3OH.