Dry　reforming　of　methane　(DRM),　which　involves　the　activation　of　inert　C-H　bonds　and　C-O　bonds,　at　mild　conditions　is　a　tremendous　challenge.　The　sluggish　mobility　of　oxygen　during　the　reaction　is　known　as　a　key　issue　causing　low　activity　and　poor　stability　of　catalysts　by　the　coke　formation.　Herein,　a　novel　Cu-CNN/Pd-BDCNN　photocatalyst　that　is　made　up　of　＇Cu-nanoparticle-loaded　g-C3N4　nanosheets＇　and　＇Pd-nanoparticle-loaded　boron-doped　nitrogen-deficient　g-C3N4　nanosheets＇　is　reported.　The　existing　dual-reaction-sites　benefit　the　reactive　oxygen　intermediates　participate　in　the　reaction　directly　without　distant　migration.　The　in　situ　characterizations　and　density　functional　theory　calculations　reveal　a　newly　dual　reaction　pathway　through　simultaneous　dehydrogenation　of　methoxy　and　methyl　intermediates,　and　demonstrate　the　importance　of　metal　loading,　which　promote　the　CO2　and　CH4　activation　from　both　aspects　of　thermodynamics　and　kinetics.　The　optimized　Cu-CNN/Pd-BDCNN　photocatalyst　displays　an　excellent　syngas　formation　rate　of　over　800 µmol g−1 h−1　with　H2/CO　=　1　and　splendid　stability　in　continuous　flow　reaction　under　300 mW cm−2　xenon　lamp　irradiation　at　room　temperature.　The　＇dual-site＇　and　＇dual-path＇　strategy　shed　light　on　the　design　of　effective　photocatalysts　for　methane　dry　reforming.　©　2023　Wiley-VCH　GmbH.