Luminescent Eu3+/Tb3+ doped mesoporous bioactive glass nanofibers (MBGNFs) with average diameter of 100–120nm were fabricated by electrospinning method. Pluronic P123 and N-cetyltrimethylammonium bromide (CTAB) were used as co-surfactants to generate porous structure of the nanofibers. N2 adsorption–desorption measurement reveals that the MBGNF:Eu3+ have a surface area of 188m2g−1, a pore volume of 0.246cm3g−1 and average pore size of 4.17nm, and the MBGNF:Tb3+ have a surface area of 171m2g−1, a pore volume of 0.186cm3g−1 and average pore size of 3.65nm. Photoluminescence measurements reveal that the MBGNF:Eu3+ show strong red emission dominated by the 5D0→7F2 transition of Eu3+ at 614nm with a lifetime of 1.356ms, and MBGNF:Tb3+ show strong green emission dominated by the 5D4→7F5 transition of Tb3+ at 544nm with a lifetime of 1.982ms. The biocompatibility tests on L929 fibroblast cells using MTT assay reveal low cytotoxicity of MBGNF. These luminescent nanofibers show sustained release properties for ibuprofen (IBU) in vitro. The emission intensities of Eu3+ in the drug delivery system vary with the released amount of IBU, thus making the drug release be easily tracked and monitored by the change of the luminescence intensity.