In the electrochemiluminescence (ECL) field, most reported luminophores were focused on high-triggering potential and short wavelength, which was adverse for the ECL theory study and application at low potentials. Perylene diimide derivatives could emit near-infrared (NIR) ECL at low-triggering potential; however, they are always highly aggregated into a microrod structure and stacked together, which largely limited their application in biological fields such as bio-sensing and bio-imaging. To overcome these obstacles, we designed a novel perylene diimide molecule, namely N,N′-dicaproate sodium-3,4,9,10-perylenedicarboximide (PDI-COONa). This molecule self-assembled into a two-dimensional network nanostructure, which largely decreased the aggregation degree of PDI molecules and provided solid bases for designing lowly-aggregated PDI molecules. Also, the formed nanoluminophore produced strong emission at −0.26 V with an NIR wavelength 700 nm, which should be due to the excited J-type PDI-COO⁻ dimers. Moreover, this network nanoluminophore well-dispersed on graphene oxide (GO) as an ECL nanomaterial to label secondary antibodies and fabricate a sandwiched immunosensor for alpha-fetoprotein (AFP) detection between 0 and −0.6 V. This immunosensor showed a wider linear response for AFP ranging from 0.1 fg mL⁻¹ to 1 μg mL⁻¹ with a low detection limit 0.0353 fg mL⁻¹ compared with other immunosensors based on PDI microrod-modified GO ECL materials. The fabricated immunosensor also showed good feasibility in human serum samples.