The synthesis and the first single crystal structure refinements of α-PbO₂, a high-pressure modification of lead dioxide, at room and low temperatures are presented (RFsigma/RFuniq 0.025/0.048, 0.028/0.047, 0.027/0.044, wRFsigma/wRFuniq 0.056/0.061, 0.059/0.063, 0.059/0.062 at 293, 203, and 113 K, correspondingly). Single crystals were grown by a hydrothermal synthesis procedure (p=4.0 GPa, temperature range 600-300 °C, cooling rate 1.25°/min). α-PbO₂ is orthorhombic, space group Pbcn (No. 60), Z=4, with a=4.9858(2) Å, b=5.9596(3) Å, c=5.4626(2) Å, V=162.31(1) Å3 for T=293 K. The description of the structure is given from a cation- and an anion-centered perspective. The oxygen atoms are coordinated by three lead atoms and oscillate mainly perpendicularly to the Pb ₃-plane. The principal axes of the thermal displacement parameters decrease under cooling, and the anisotropy of the thermal oscillations increases from 293 to 113 K. Anisotropic thermal expansion was observed. Upon heating, the crystal structure extends practically only along the a-axis.