In recent years, gold nanoparticles (AuNPs) have attracted much attention due to their ease of surface modification, excellent biocompatibility, and extraordinary optoelectronic and catalytic activities. Herein, based on a AuNP-catalyzed reaction, a strategy for tailoring luminescent molecules in situ is proposed to trigger an ultrastrong chemiluminescence (CL). In the strategy, flower-like AuNPs are prepared using CL molecular probes (Probe-OH for NaClO/ONOO-) via one-pot synthesis and subsequently act as a tailor for Probe-OH to generate novel CL molecules, allowing a synergistic CL enhancement about 4 times that of initial Probe-OH. Furthermore, by modification with poly(vinylpyrrolidone) (PVP) on the surface, the CL signals (only for NaClO) are amplified by 100 times based on an intermolecular chemically initiated electron exchange luminescence (CIEEL) mechanism. Given the improved sensitivity and selectivity over Probe-OH, the thus-formed CIEEL nanoplatform (PVP-Au) is successfully developed for detecting NaClO in a wide range of 2.5-100 μM, and the detection limit is 10.68 nM. This work provides unprecedented perspectives for expanding this facile and effective strategy for CL amplification based on AuNP catalysis.