The improvement and regulation of catalytic performance of nanozyme have long been pursued with sustained efforts. Herein, gold nanoparticles (S-CDs/AuNPs) with weak peroxidase-like (POD) activity were synthesized by Au-S bond using a sulfur doped carbon dots (S-CDs) as reducing agent and stabilizer. However, methylmercury (MeHg+) could selectively and sensitively regulate the POD-like activity of S-CDs/AuNPs. The catalytic activity of S-CDs/AuNPs was significantly activated with the addition of MeHg+, resulting in a significant enhancement of electromagnetic fields to present an obvious SERS signal. More intriguingly, the introduction of ochratoxin A (OTA) could simultaneously turn off the UV–vis absorbance signals and the surface-enhanced Raman scattering (SERS) signal. Based on these findings, a selective colorimetric-SERS dual-mode OTA detection strategy was established with gold amalgamation (Au@HgNPs) as the probe, and the low limit of detection (LOD) of OTA was 0.29 µgL−1 (Colorimetric) and 0.16 µgL−1 (SERS), respectively, with good recoveries from 95.9 to 104.0% (Colorimetric) and from 96.7 to 108.9% (SERS), respectively. The work paves a new way to design nanozyme-based colorimetric and SERS protocol for traces OTA residues analysis in foodstuff analysis.