Luminescent Cu nanoclusters (NCs) are potential phosphors for illumination and display, but the difficulty in achieving full-color emission greatly limits practical applications. On the basis of our previous success in preparing Cu NC self-assembly architectures with blue-green and yellow emission, in this work, Cu NC self-assembly architectures with strong red emission are prepared by replacing alkylthiol ligands with aromatic thiols. The introduction of aromatic ligands is able to influence the ligand-to-metal charge transfer and/or ligand-to-metal-metal charge transfer, thus permitting the tuning of the emission color and enhancing of the emission intensity. The emission color can be tuned from yellow to dark red by choosing the aromatic ligands with different conjugation capabilities, and the photoluminescence quantum yield is up to 15.6%. Achieving full-color emission Cu NC self-assembly architectures allows the fabrication of Cu NC-based white light-emitting diodes.