High-efficiency chemiluminescence (CL) resonance energy transfer (CRET) can be obtained by shortening the donor-acceptor distance and/or improving the luminescence efficiency of CRET acceptors. However, careful design and stringent experimental conditions are usually required for the ordered assembly of CRET acceptors on support materials to avoid aggregation-caused quenching problems. In this work, an aggregation-induced emission (AIE)-active fluorophore was disorderly adsorbed on the surface of layered double hydroxides (LDHs), which could exhibit high-efficiency luminescence. On the other hand, the positively charged LDHs can further adsorb peroxynitrite (ONOO-) on the surface of LDHs. Therefore, the LDH-supported AIE fluorophore could dramatically amplify weak CL signals from ONOO- donors as a result of ultra-high CRET efficiency by coupling the shorter donor-acceptor distance with efficient CRET acceptors. The proposed CL system has been successfully applied for the detection of NaNO2 in the concentration range from 1.0 to 100 μM with a detection limit as low as 0.5 μM. Satisfactory recoveries (98-106%) and good accuracy were achieved for sausage samples. Our success will open new avenues for the convenient design of high-efficiency CRET systems.