An electrospun poly(acrylonitrile-co-acrylic acid) nanofiber mat (PAN-co-PAA(nfm)) was successfully collected on the surface of a glassy carbon electrode (GCE). Scanning electron microscope (SEM) images showed that the porous electrospun mat was composed of similar to 160 nm diameter of uniform knitted nanofibers. The cationic luminescence probe, tris(2,2'-bipyridyl)ruthenium(II) complex ([Ru(bpy)(3)](2+)), was innovatively and first incorporated into the negatively charged PAN-co-PAA(nfm)-modified GCE via electrostatic interaction. Compared with the [Ru(bpy)(3)](2+) immobilized on normal PAN-co-PAA deposited coating, [Ru(bpy)(3)](2+)/PAN-co-PAA(nfm) exhibited dramatically enhanced electrochemical and electrochemiluminescence (ECL) performances, namely, more than 100 times higher ECL intensity could be feasibly obtained via the electrospinning technique.