We obtained germanium dioxide (GeO2) whiskers in bulk quantity by ablating a germanium target at 820 °C with a pulsed KrF excimer laser in an argon atmosphere. Most of the GeO2 whiskers were smooth and straight with hexagonal or triangular, or quadrilateral cross sections while some of them had a bamboo-shoot-shaped form. Results of scanning electron microscopy, transmission electron microscopy, and x-ray diffraction showed that the whiskers are hexagonal crystalline GeO2.