Photon upconversion (UC) process is an anti-Stoke emission, which enables the sequential absorption of two or more lower energy of excitation NIR light to higher energy of luminescent emission via intermediate excited electronic states. [1][2][3][4] The typical upconversion nanocrystals (UCNCs) is NaYF 4 single crystalline hexagonal phase host matrix co-doped with sensitizer (donor) Yb 3+ and activator (acceptor) Er 3+ rare earth trivalent lanthanide ions. 2 The UCNCs are promising luminescent nanomaterials which exhibit peculiar physiochemical attributes, including large anti-Stoke shift, minimal autofluorescence background, narrow emission bandwidths, deep penetration depth into tissue sample, and low cytotoxicity 2,4,5 . UCNCs have a limitation of the very low intrinsic photon conversion efficiency typically lower than 1% owing to the low extinction coefficient of lanthanide dopants. 6 The plasmonic nanostructure array can be exploited to enhance the electric field and light absorption in coupling of the external EM field mediated by localized surface plasmon (LSP). [7][8][9] The LSP resonance frequency of the plasmonic devices can be easily tuned by modifying the size, shape, compositions, the effective index of the dielectric environment. 7 By coupling the plasmonic nanostructures array with the UCNCs film, the light absorption enhancement at the NIR-excitation wavelength followed by radiative decay rate and light-emission enhancements could be overcome the intrinsic low quantum yield of the UCNCs.In this study, numerical investigation was performed on the gold nanocavity array 10 enclosed by a UCNCs layer on a silver film substrate to enhance the upconversion luminescence (UCL). The possible fabrication details of the plasmonic nanocavity array substrate are demonstrated in PART I of the Supporting Information.The plasmonic response of the pNCA (defined as a pNCA) was analyzed by a finite-difference time-domain (FDTD) method to scrutinize the optical origin of the UCL enhancement. With the precisely tuning of the design parameter such as a wall thickness of the plasmonic nanocavity, suggested plasmonic platform enables inducing a strong intense light entrapment responsible for the LSP at the absorption spectra peak of the UCNCs. Figure 1(a), UCNCs encapsulated plasmonic gold nanocavities arranged on a silver back-reflective film substrate (defined as a pNCA) is suggested. This pNCA platform is able to capture the incoming external EM field around the nanocavity configuration at specific wavelengths range arising from the LSP effect, which leads to a strong near field confinement and light absorption inside the UCNCs layer. In case that the x-polarized plane wave light source with a broadband wavelength range (λ = 400-1200 nm) is impinged onto the pNCA substrate, an optical simulation model of the periodic pNCA with a rectangular lattice is described in Figure 1(b). The detailed optical simulation setup and refractive indices used in the simulation for the pNCA platform can be referred to PART II and PART II...