In this paper, bimetallic CuCo Prussian blue analogue (CuCo PBA) nanocubes, synthesized through a self-assembly method, were found to induce chemiluminescence (CL) of luminol-NaOH since the catalytic oxidation activity of CuCo PBA. The CL intensity of luminol-NaOH system was enhanced about 50 times with the addition of CuCo PBA. When uric acid (UA) was added to the new luminol-NaOH-CuCo PBA system, the CL signal could be reduced significantly. Based on these, an enzyme-free CL sensor was constructed for UA detection with a linear response range from 0.30 to 5.00 μM, and detection limit of 0.16 μM (S/N = 3). The other common species in human serum didn’t affect UA detection. Furthermore, this CL sensor was successfully applied to detect the UA in human serum samples with high sensitivity. This work not only discovered the enzyme-like properties of CuCo PBA, but also broadened its application in CL bioassays.