Good quality and perfectly stoichiometric GeO2 layers are promising interlayers to be implemented in alternative devices based on high dielectric constant oxide/Ge(100). In this work, the authors report on the growth by atomic layer deposition of GeO2 films using a divalent Ge precursor combined with O3. The films are composed of smooth and perfectly stoichiometric GeO2. The contamination level is extremely low. The deposited GeO2 films have a band gap of 5.81±0.04eV. The conduction and valence band offsets at the GeO2∕Ge heterojunction are found to be 0.6±0.1 and 4.5±0.1eV, respectively.