Liquid crystals (LCs) are a very important display material. However, the use of LC, especially LC loaded nanoparticles, as a catalyst to amplify analytical signal and coupled with specific aptamer (Apt) as recognition element to construct a highly sensitive and selective three-mode molecular spectral assay is rarely reported. In this article, five LCs such as cholesteryl benzoate (CB) were studied by molecular spectroscopy to indicate liquid crystal nanoparticles in the system, and highly catalysis and stable CB loaded-nanosilver (CB@AgNPs) sol was prepared. The slope procedure was used to study the catalysis of the five LCs and CB@AgNPs on the new indicator reaction between AgNO3 and sodium formate (Fo) to produce silver nanoparticles (AgNPs) with a strong surface plasmon resonance absorption (Abs) peak at 450 nm, resonance Rayleigh scattering (RRS) peak at 370 nm and surface enhanced Raman scattering (SERS) peak at 1618 cm− 1 in the presence of molecular probes. By coupling the new CB@AgNPs catalytic indicator reaction with the Apt reaction, a new CB@AgNPs catalytic amplification-SERS/RRS/Abs trimode biosensoring platform was constructed for detecting for inorganic pollutants such as Pb2+, Cd2+, Hg2+ and As3+.