Ordered, hierarchical structures formed from nanoparticle (NP) self-assembly are of interest as they display the synergistic properties of the individual NP. Herein we report a one-pot approach to form and self-assemble gold (Au) nanoplatelets into brick-wall like (BWL) Au superparticles (AuSPs). We employ an aniline (ANI) derivative, N-(3-amidino)-aniline (NAAN) to reduce the Au precursor into Au nanoplatelets in the presence of Br-1. The corresponding oxidation product, poly (N-(3-amidino)-aniline) (PNAAN) functions as the capping agent and enables the face-to-face self-assembly of Au nanoplatelets into BWL AuSPs via the p-p stacking interaction. Systematically tuning the reaction conditions leads to spherical, mushroom- or cauliflower-like AuSPs. The significant electromagnetic enhancement of AuSPs via the formation of the nanogaps produces high-density hotspots for excellent surface-enhanced Raman scattering (SERS) enhancement, enabling the ultrasensitive SERS assay with detection limit of pM. Moreover, the as-prepared AuSPs exhibited the intense SERS signals under laser excitation with different wavelength and the excellent reproducibility after long-duration exposure in different media. The developed SERS sensor has a great potential for a wide application of bioanalysis, clinic assays and environmental monitoring. (C) 2020 Elsevier Inc. All rights reserved.