In this paper, a novel chemiluminescence (CL) system was constructed based on the oxidizing properties of Fe-Co-Co. Fe-Co-Co, a prussian blue analogue (PBA), can significantlyenhance the CL intensity of luminol under alkaline conditions more than 95 times without the addition of other oxidants. Moreover, the CL intensity of luminol-Fe-Co-Co system is 29 times higher than that of the luminol-potassium ferricyanide (K3[Fe(CN)6]) system, because of the synergy of bimetals and the catalytic performance of nanomaterials. When adding dopamine (DA) into this new system, the CL intensity decreased. Based on this, we developed a new method to detect DA. The signal intensity of the chemiluminescence system is linearly related to the concentration of DA in the range of 0.1–5.0 μM, and the detection limit of DA is 0.06 μM. Finally, this CL method has been successfully used for the determination of DA in human serum samples.