Metal-organic framework (MOF) MIL-101 and surface plasmon polariton (SPP) supported gold nanoparticles (Au NPs) hybrid systems were developed as a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) detection platform, in which a green electrostatic self-assembly technology was adopted to construct the substrate. In an aqueous solution, the electronegativity of the particles can be used to prepare the composite substrate without any surface modifier. Due to the enrichment capacity of MIL-101 and the electromagnetic enhancement from Au NPs, the well-designed MIL-101/Au composites possessed ultrahigh sensitivity with the detection limit of Rhodamine 6G (R6G) as low as 10^-10 mol·L^-1. Meanwhile, the substrate exhibits high stability, excellent reproducibility, and recyclability. Additionally, the novel substrate can be explored for direct capture, and sensitively detect pesticide residues such as thiram.