The　selective　partial　oxidation　of　methane　to　methanol　using　molecular　oxygen　(O2)　represents　a　long-standing　challenge,　inspiring　extensive　study　for　many　decades.　However,　considerable　challenges　still　prevent　low-temperature　methane　activation　via　the　aerobic　route.　Here　we　report　a　precipitated　Pd-containing　phosphomolybdate,　which,　after　activation　by　molecular　hydrogen　(H2),　converts　methane　and　O2　almost　exclusively　to　methanol　at　room　temperature.　The　highest　activity　reaches　67.4　μmol　gcat−1　h−1.　Pd　enables　rapid　H2　activation　and　H　spillover　to　phosphomolybdate　for　Mo　reduction,　while　facile　O2　activation　and　subsequent　methane　activation　occur　on　the　reduced　phosphomolybdate　sites.　Continuous　production　of　methanol　from　methane　was　also　achieved　by　concurrently　introducing　H2,　O2　and　methane　into　the　system,　where　H2　assists　in　maintaining　a　moderately　reduced　state　of　phosphomolybdate.　This　work　reveals　the　underexplored　potential　of　such　a　Mo-based　catalyst　for　aerobic　methane　oxidation　and　highlights　the　importance　of　regulating　the　chemical　valence　state　to　construct　methane　active　sites.　[Figure　not　available:　see　fulltext.].　©　2023,　The　Author(s),　under　exclusive　licence　to　Springer　Nature　Limited.