Cyanides, which are extremely toxic chemicals that are rapidly absorbed into the human body and interact with cytochrome oxidase, strongly inhibit cellular respiration to body death with convulsions. Cyanide ions that exist in many forms in nature such as those found in apricot kernels, cassava roots, and bamboo shoots as cyanogenic glycosides are inevitably used in various industries, including gold and silver mining as well as in dyes and plastic industries. In this study, for the sake of developing ultrahigh-sensitive sensors for cyanide monitoring in a simple manner, we chemically synthesize Au core −Ag shell hybrid nanomaterials of different core/shell thicknesses for colorimetric sensors and fiber optical sensors. Their sensing principle relies on the formation of the Ag/Au cyanocomplex upon cyanide injection. The generated metal cyanocomplex induced changes in refractive indices, causing changes in properties of localized surface plasmon resonance (LSPR), i.e., optical absorbance change for the colorimetric sensors. For fiber optical sensors, the hybrid metal nanoparticles were immobilized on the fiber core surface and the metal cyanocomplex formation induced changes in the fiber cladding refractive index, enabling quantitative cyanide detection with ultrahigh sensitivity. The LSPR-based colorimetric sensor provided the lowest detectable cyanide concentration of 5 × 10 −6 M, whereas the value for the fiber-based sensor was 8 × 10 −11 M.