Peptides are an important recognition element for small molecules and have been used in the field of biologicalanalysis. However, it has been rarely reported that a novel method combining peptides as recognitionelements with covalent organic framework (COF) as catalytic amplification signal to constructhighly sensitive and selective three-mode molecular spectroscopy. In this paper, high catalytic and stablethree COFs were prepared, and the catalysis of the new indicator nanoreaction of HAuCl4-sodiumformate(Fo) was studied by molecular spectral slope procedure. The produced gold nanoparticles (AuNPs) exhibita strong resonance Rayleigh scattering (RRS) peak at 370 nm and surface plasmon resonance absorption(Abs) peak at 540 nm. In the presence of molecular probes, a strongest surface-enhanced Raman scattering(SERS) peak was generated at 1617 cm1. Combining the COFTpBD amplification indicator reactionwith specific peptide (PT) reaction of Cu2+, a novel, sensitive and selective SERS/RRS/Abs assay platformwas established, with a SERS linear range of 0.005–0.115 nmol/L Cu2+. In addition, the two workingcurves of lg[Cu2+] vs SERS and [Cu2+] vs SERS intensity, and the nanocatalytic mechanism were discussed.