In pH 2.55 HCl solution, vitamin C (VC) could deoxidize [Fe(CN) 6 ] 3− producing [Fe(CN) 6 ] 4− , which reacted with Zr (IV) to form Zr[Fe(CN) 6 ] complex, then aggregated to produce {Zr[Fe(CN)6]} n nanoparticles by virtue of hydrophobic force and van der Waals force. The intensity of RRS at 340 nm is directly proportional to the concentration of VC in the range of 0.1-1.45 μg mL −1 , and the detection limit (3 s/k) is 0.128 ng mL −1 . In this work, the spectral characteristics of RRS, the optimum condition, the reaction mechanism of the reaction, and their influencing factors especially the effect of organic solvent have been studied. The sensitive, rapid, and simple method based on resonance Rayleigh scattering was successfully applied to determine trace amount VC in VC injection and tablet.