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In this work, Ag nanoparticle/Ag-doped SiO₂ composite films were prepared with AgNO₃ and tetraethoxysilane precursors through a simple and environmentally friendly sol–gel method under high annealing temperatures. The effect of different annealing temperatures (400${}^{\circ }$C, 500${}^{\circ }$C, 600${}^{\circ }$C, and 700${}^{\circ }$C) on the structural and optical characters of the composite films was investigated. The localized surface plasmon resonance (LSPR) effect of the Ag nanoparticle/Ag-doped SiO₂ composite films enhanced the fluorescence intensity of CdSe quantum dots (QDs). Scanning electron microscopy (SEM), UV-vis spectrophotometer and photoluminescence (PL) spectroscopy were used to characterize the morphology and optical properties of the composite nanostructure.