Luminescent, mesoporous, and bioactive europium-doped hydroxyapatite (HAp:Eu3+) nanofibers and microbelts have been prepared by a combination of sol–gel and electrospinning processes with a cationic surfactant as template. The obtained multifunctional hydroxyapatite nanofibers and microbelts, which have mesoporous structure and red luminescence, were tested as drug carriers by investigating their drug-storage/release properties with ibuprofen (IBU) as model drug. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution (HR) TEM, FTIR spectroscopy, N2 adsorption/desorption, photoluminescence (PL) spectra, and UV/Vis spectroscopy were used to characterize the structural, morphological, textural, and optical properties of the resulting samples. The results reveal that the multifunctional hydroxyapatites exhibit irregular mesostructure, and have fiberlike and beltlike morphologies with sizes of several hundred nanometers in width and several millimeters in length. The IBU-loaded HAp:Eu3+ system shows red luminescence of Eu3+ (5D0–7F0,1,2) under UV irradiation and controlled release of IBU. In addition, the emission intensity of Eu3+ in the drug carrier system varies with the released amount of IBU, and thus drug release can be easily tracked and monitored by the change in luminescence intensity.