Graphitic-phase carbon nitride (g-C 3 N 4 ) materials have exhibited increasingly remarkable performance as emerging electrochemiluminescence (ECL) emitters, owing to their unique optical and electronic properties; however, the ECL merits of porous g-C 3 N 4 nanofibers doped with ternary metals are not yet explored. Deciphering the ECL properties of trimetal-doped g-C 3 N 4 nanofibers could provide an exquisite pathway for ultrasensitive sensing and imaging with impressive advantages of minimal background signal, great sensitivity, and durability. Herein, we rationally synthesized g-C 3 N 4 nanofibers doped atomically with Mn, Fe, and Co elements (Mn/Fe/Co/g-C 3 N 4 ) in a one-pot via the protonation in ethanol and annealing process driven by the rolling up mechanism. The ECL performance of g-C 3 N 4 with and without metal dopants was investigated and compared with standard Ru(bpy) 3 2+ in the presence of potassium persulfate (K 2 S 2 O 8 ) as the coreactant. Notably, g-C 3 N 4 nanofibers doped with metal ions exhibited an ECL efficiency of 483% that was 4.83 times higher than that of Ru(bpy) 3 2+ . Mechanistic investigations unveiled that the g-C 3 N 4 nanofibers possess a large surface area and, as a result, exhibit a reduced interfacial impedance within the porous microstructure. These factors contribute to the acceleration of charge transfer rates and the stabilization of charge carriers and excitons, ultimately facilitating the ECL process. This research endeavor may pave the way for a new hot research area and serves as a powerful tool for elucidating fundamental inquiries of ECL on one-dimensional g-C 3 N 4 nanostructures.