A convenient and sensitive resonance Rayleigh scattering (RRS) method for the detection of chitosan (CTS) has been developed via forming Cu-Zn supramolecular complex by complexation reaction, hydrophobic force and electrostatic attraction. The microstructure of the complex was characterized by FT-IR, zeta potential, scanning electron microscope (SEM), UV–vis and RRS. Furthermore, the interaction mechanism among Cu(II), Zn(II), CTS and sodium dodecyl benzene sulfonate (SDBS) was studied. The results revealed that CTS and Cu(II) or Zn(II) formed a supramolecular complex with RRS enhancement in weak acid condition. In the presence of SDBS, the RRS intensity of CTS-Cu(II)-SDBS or CTS-Zn(II)-SDBS was significantly higher than that of the binary system without SDBS at the same CTS concentration. The RRS intensity of CTS-Cu(II)-Zn(II)-SDBS was higher than that of CTS-Cu(II)-SDBS and CTS-Zn(II)-SDBS. The RRS intensity increased linearly with the increase of CTS concentration made it possible to determine CTS quantitatively. In the range extending from 0.10 to 5.00 μg/mL, the equation of linear regression was ΔI=1848.8c-138.3 with a correlation coefficient 0.9996, and the detection limit was estimated to be 37.96 ng/mL. The study was successfully applied for the determination of CTS in health food samples, suggesting its great potential toward CTS analysis.