The enhancement of the plasmonic signatures, indicated by the shifting of the localized surface plasmon resonances, of three-dimensional, hollow, gold nanocages with respect to substrate nature and cage density is reported. The effect of substrate nature was investigated using absorbance, reflection, and transmission by ultraviolet-visible and near-infrared spectrophotometry. The gold nanocages were deposited on substrates as monolayers primarily by Langmuir-Blodgett technique. The density of the deposited monolayers and the nature of the surface of the substrates were determined using AFM and SEM/TEM imaging. The position of the LSPR signatures, primarily the dipolar plasmonic resonances, with respect to changing environment and nanostructure characteristics determined the tuneability of the plasmonic enhancements.