In the face of the current urgent food safety situation, the qualitative detection of trace amounts of illegal food additives is of great significance. The Hollow Core Photonic Crystal Fiber Surface-Enhanced Raman Scattering (HCPCF SERS) based sensing system was proposed to achieve qualitative detection of melamine. The system adopted the reverse-direction light collection scheme, and the silver SERS substrate was produced by ion sputtering, and the PCF taper was selectively filled, and the output signal was collected by the spectrometer. The proposed system was utilized to detect melamine liquid sample qualitatively, the distinct SERS spectrum of melamine was acquired, and the detection limit is 0.25 g/L. The experimental results showed that the sensing system can achieve trace qualitative detection of melamine.