Metal nanoclusters exhibit unusual optical and catalytic properties due to their unique lectronic structures. Here, surfactant-free silver nanoclusters supported on carbon nanodots were synthesized through a facile and green approach with only glucose and AgNO3 as precursors and without any other protecting ligands and reducing agents. The hybrid nanoclusters exhibited enhanced blue fluorescence compared to the carbon nanodots. More importantly, the “surface-clean” silver nanoclusters have remarkable   featured with the most efficient four-electron transfer process. Moreover, compared with commercial Pt/C catalyst, the Pt-free hybrid clusters showed comparable catalytic performance for ORR but much higher tolerance to methanol crossover. Such silver nanoclusters will provide broad applications in fluorescence-related areas and in fuel cells as an efficient Pt-free catalyst with low cost and high catalytic performance.