Electronic coupling can be used to tailor electronic states and optical properties of the luminophores. Therefore, electronically coupled systems would provide unique properties, which cannot be achieved by individual constituents. Here, electronically coupled gold nanoclusters (AuNCs) were prepared on the basis of organosilane grafting and a sol–gel-derived porous silica template. After prolonged drying, the formed AuNCs@silica composites exhibited red-shifted, line-width-narrowed, deep-red emission with high quantum yields (QYs) of ∼66% due to electronic-coupling-enhanced radiative rates and covalent-bonding-suppressed nonradiative relaxation. Meanwhile, the absorption maximum was slightly blue-shifted, leading to a large Stokes shift. All experimental findings revealed the formation of electronically coupled AuNC aggregates confined inside the nanopores and bonded to silica matrix. The mechanism is distinctly different from conventional aggregation-enhanced emission. Our work would provide great potential to engineer photophysical properties by controlling the packing modes.