Amorphous silica shells, used for functionalization of inorganic nanoparticles in bioapplications, were coated on chemically synthesized NaYF4:Yb,Er upconversion fluorescent nanoparticles via a reverse microemulsion method by using dual surfactants of polyoxyethylene (5) nonylphenylether and 1-hexanol, and tetraethyl orthosilicate as precursor. NaYF4:Yb,Er nanoparticles were equiaxed with a particle size of 11.1 ± 1.3 nm. The thickness of silica shell was ∼8 nm. NaYF4:Yb,Er/silica core/shell nanoparticles were well dispersed in solvents such as ethanol and deionized water. The emission intensities of NaYF4:Yb,Er/silica core/shell nanoparticles remained the same as that of uncoated nanoparticles after surface functionalization with an amine group using (3-aminopropyl)-trimethoxysilan. Silica, although providing a good barrier to the nonradiative relaxation between the upconversion nanoparticles and the environments, did not enhance the emission intensity of upconversion nanoparticles. To increase the emission intensity of NaYF4:Yb,Er/silica core/shell nanoparticles, an undoped NaYF4 shell (∼3-nm thick) was deposited on the upconversion nanoparticles before the silica coating. The total emission intensity of NaYF4:Yb,Er/NaYF4/silica core/shell/shell nanoparticles increased by 15 times compared to that without the intermediate NaYF4 shell. The critical shell thickness of NaYF4 was ∼3 nm, beyond which no further emission intensity enhancement was observed.