AbstractUniformly sized and shaped Eu3+‐doped silica nanowires were conventionally fabricated by the microemulsion method accompanied with a sol–gel process for the first time. The products were characterized by different techniques, and their luminescence properties were investigated and compared. The scanning electron microscopy and transmission electron microscopy images demonstrated that the as‐synthesized Eu3+‐doped silica nanowires were formed in high yield with a smooth surface and a uniform diameter of about 130–150 nm. The results of FTIR spectroscopy, energy‐dispersive spectroscopy, and X‐ray diffraction showed that the Eu3+ ions were doped into the silica network structure in the form of Si–O–Eu bonds. The effect of the Eu3+ concentration on the luminescent intensity was investigated, and the highest emission intensity was found at the composition of 20 mol‐% Eu3+. The obtained Eu3+‐doped silica nanowires exhibited characteristic luminescent emission of Eu3+ at λ = 613 nm and apparent concentration quenching above the concentration of 20 mol‐% Eu3+. The growth processes of the silica nanowires were explained in detail on the basis of a modified vapor–liquid–solid mechanism.