Up‐conversion (UC) luminescent porous silica fibers decorated with NaYF4:Yb3+, Er3+ nanocrystals (NCs) (denoted as NaYF4:Yb3+, Er3+@silica fiber) are prepared by the electrospinning process using cationic surfactant P123 as a template. Monodisperse and hydrophobic oleic acid capped β‐NaYF4: Yb3+, Er3+ NCs are prepared by thermal decomposition methodology. Then, these NCs are transferred into aqueous solution by employing cetyltrimethylammonium bromide (CTAB) as secondary surfactant. The water‐dispersible β‐NaYF4:Yb3+, Er3+ NCs are dispersed into precursor electrospinning solution containing P123 and tetraethyl orthosilicate (TEOS), followed by preparation of precursor fibers via electrospinning. Finally, porous α‐NaYF4:Yb3+, Er3+@silica fiber nanocomposites are obtained after annealing the precursor fibers containing β‐NaYF4:Yb3+, Er3+ at 550 °C. The as‐prepared α‐NaYF4:Yb3+, Er3+@silica fiber possesses porous structure and UC luminescence properties simultaneously. Furthermore, the obtained nanocomposites can be used as a drug delivery host carrier and drug storage/release properties are investigated, using ibuprofen (IBU) as a model drug. The results indicate that the IBU–loaded α‐NaYF4:Yb3+, Er3+@silica fiber nanocomposites show UC emission of Er3+ under 980 nm NIR laser excitation and a controlled release property for IBU. Meanwhile, the UC emission intensity of IBU–α‐NaYF4:Yb3+, Er3+@silica fiber system varies with the released amount of IBU. Electrospinning derived α‐NaYF4:Yb3+, Er3+ decorated silica fibers, which combine porous structure and red up‐conversion luminescence, can be used as a drug‐delivery vehicle. The IBU‐loaded silica fiber system shows a controlled release property for IBU. In addition, the up‐conversion emission intensities of the drug carrier system vary with the amount of IBU released.