The solid state of adefovir dipivoxil (AD) has been revisited. In the present article we extend the knowledge about the solid state of this pharmaceutical prodrug. The stability landscape of the amorphous form with respect to the anhydrous and hydrate crystalline forms has been studied, and the use of an antiplasticizing agent to increase its Tg is described. The crystal structure of the elusive anhydrous form I has been determined from laboratory powder X-ray diffraction data by means of direct space methods using the computing program FOX. In addition, three new isostructural solvates of AD (methanol, ethylenglycol, and methylethylketone) have been discovered and structurally characterized by single crystal X-ray diffraction.