Plasmonic enhancement of photoluminescence from bulk silicon was achieved by spectrally tailoring coupled localized surface plasmon resonance (LSPR) in the Al2O3 cover/nanostructured platinum (nano-Pt)/Al2O3 spacer/silicon multilayer structures prepared by atomic layer deposition (ALD). Agreement between the simulation and experimental data indicates that the plasmonic activity originates from absorption enhancement due to coupled LSPR. Because of the optimized dielectric environment deposited by ALD around the nano-Pt layer, absorption of the multilayer structure was enhanced by the precise tuning of coupled LSPR to coincide with the excitation wavelength. This accurate plasmonic multilayer structure grown by ALD with high precision, tunability, uniformity, and reproducibility can be further applied in efficient light-emitting devices.