Millimeter-scale 3D superlattice arrays composed of dense, regular, and vertically aligned gold nanorods are fabricated by evaporative self-assembly. The regular organization of the gold nanorods into a macroscopic superlattice enables the production of a plasmonic substrate with excellent sensitivity and reproducibility, as well as reliability in surface-enhanced Raman scattering. The work bridges the gap between nanoscale materials and macroscopic applications.