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 beta-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 beta-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 alpha-NaYF4:Yb3+, Er3+@silica fiber nanocomposites are obtained after annealing the precursor fibers containing beta-NaYF4:Yb3+, Er3+ at 550 degrees C. The as-prepared alpha-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 alpha-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-alpha-NaYF4:Yb3+, Er3+@silica fiber system varies with the released amount of IBU.