A high‐performance Au@MIL‐101/PMMA/DT surface‐enhanced Raman scattering (SERS) substrate was fabricated for sensitive and stable detection of paraquat by self‐assembling metal organic framework–modified Au nanoparticles (Au@MIL‐101) on a poly(methyl methacrylate) (PMMA) film and then immobilizing the formed substrate onto a duct tape (DT). The highly closely packed Au@MIL‐101 array provided intensive hotspots for SERS sensing. The MIL‐101 layer modified on the surface of Au nanoparticles could absorb paraquat to the electromagnetic enhancement area of Au nanoparticles. The DT on the bottom made the substrate smoother, which is beneficial for achieving a more stable detection performance. As a result, the constructed substrate exhibited outstanding uniformity with relative standard deviations of 9.47% and storage stability for 2 months. For detecting paraquat, the substrate showed a low detection limit of 7.1 × 10−9 M (1.83 µg/kg) and wide linear range from 10−8 to 10−2 M. Furthermore, the substrate showed good detection performance in real cereal samples with desirable recovery rates from 91.57% to 102.32%.