Graphene oxide (GO) was for the first time designed as a bionanolabel for sensitive chemiluminescent (CL) immunosensing of human IgG by taking advantage of a magnetic separation–mixing process and a GO-triggered luminol–H2O2 CL reaction. The detection limit of the concentration of human IgG is 1.2 pg mL−1, which is comparable with or better than other immunoassays.