A novel concave cone surface-enhanced Raman scattering (SERS) fiber probe modified with the gold nanoparticles was demonstrated. We studied the preparation method of the concave cone fiber probes, analyzed the relationship between the morphology of the probe and the corrosion time, modified the gold nanoparticles onto the inner surface of the concave cone by the chemical self-assembly method, and tested the SERS detection performance of the prepared probe. Experimental results show that the concave cone fiber probe has a lower fiber Raman background, about 1/3 of the tapered probe prepared with the same fiber. With 633 nm excitation, Raman spectra of rhodamine 6G (R6G) aqueous solution of 100 nmol/L can be detected by the concave cone fiber probes modified with gold nanoparticles. Due to this concave cone structure, the metal nanoparticles are more difficult to fall off, and the probe has better damage resistance. Based on the above advantages, this type of concave cone fiber probe may have potential application value in the field of SERS remote detection.