In this work, electrogenerated chemiluminescence resonance energy transfer (ECL-RET) between luminol as a donor and CdSe@ZnS quantum dots (QDs) as an acceptor was reported in neutral conditions. It was observed that a glassy carbon electrode modified with CdSe@ZnS quantum dots (CdSe@ZnS/GCE) can catalyze the luminol oxidation to promote the anodic luminol ECL without coreactants. The intensity of anodic luminol ECL (0.60 V) at the CdSe@ZnS/GCE was enhanced more than 1 order of magnitude compared with that at the bare GCE. Another stronger anodic ECL peak observed at more positive potential (1.10 V) could be assigned to the ECL-RET between the excited state of luminol and the QDs. A label-free ECL aptasensor for the detection of thrombin was fabricated based on the synergic effect of the electrocatalysis and the ECL-RET. The approach showed high sensitivity, good selectivity, and wide linearity for the detection of thrombin in the range of 10 fM-100 pM with a detection limit of 1.4 fM (S/N = 3). The results suggested that the as-proposed luminol-QDs ECL biosensor will be promising in the detection of protein.