Accelerating the charge transfer between electroactive species and the electrode is always a hot topic. Here, we report a finding of Ru(bpy)33+ diffusion-induced acceleration of charge transfer from Ru(bpy)32+-doped silica nanoparticles (RDSNs) to the electrode via electrochemiluminescence (ECL) imaging at a single nanoparticle scale. Ru(bpy)32+ in the electrolyte can act as an enhancer of RDSN ECL emission in the presence of coreactant tripropylamine, which amplifies the RDSN ECL by 478 times at 10 μM free Ru(bpy)32+. According to percolation theory, the diffusion of electro-generated Ru(bpy)33+ near a single RDSN brings much quicker charge transfer to the electrode than electron hopping in RDSN, which is demonstrated by spatial and temporal interaction imaging of the RDSN and the Ru(III) diffusion layer. Taking advantage of this new mechanism, a real-time ECL imaging method has been constructed to monitor the rapid change of cell permeability during surfactant treatment.