Al18B4O33:Eu3+, Tb3+ whiskers have been successfully prepared by a simple gel nano-coating method using aluminum isopropoxide as the starting materials. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL), and thermogravimetric analysis (TGA) were used characterize the samples. The results show coexistence of the crystal phase Al18B4O33, amorphous phase, and Eu3+, Tb3+ ions of the samples with initial addition Al/B ratios from 3 to 1 are incorporated into the amorphous phase. The Al18B4O33:Eu3+, Tb3+ whiskers are very straight with an average diameter of 600 nm and lengths ranging from 5 to 10 mu m. Under ultraviolet excitation at 365 nm, samples show mainly exhibit the characteristic emission of Eu3+ corresponding to D-5(0) -> F-1,F-2 transitions due to an efficient energy transfer occurs from Tb3+ to Eu3+.