摘要： Most electrochemiluminescence (ECL) studies were focused on the single emission of luminophore, which was severely limited the development of multi-color ECL fundamental theory and applications. Herein, we prepared a multi-color ECL supramolecular nanomaterial self-assembled by 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and aniline (An) through hydrogen bonding. This PTCDA-An supramolecular nanomaterial simultaneously produced multi-color emission peaked at 486, 692 and 760 nm with K2S2O8 as coreactant. And the multi-emissions were assigned to excitated PTCDA monomer (486 nm), H-dimer (692 nm) and J-dimer (760 nm). The simultaneously increased dual-color ECL intensity significantly enhanced the total ECL intensity of PTCDA-An. And this high efficient ECL nanomaterial was further used as ECL platform to construct label-free immunosensor for tumor markers carcinoembryonic antigen (CEA) detection. The total ECL intensity of immunosensor exhibited a sensitive decrease due to the simultaneously decreased ECL of multi-emissions. And this immunosensor exhibited wide linear range from 1 pg mL-1 to 10 μg mL-1 with low detection limit of 0.23 pg mL-1. Multi-color ECL from the same luminophore PTCDA in this work also provided a new perspective for multi-color ECL biomaterial’s design.