Organic-inorganic hybrid GeOx/ethylenediamine (EDA) nanowires are fabricated via a Fe2O3-assisted hydrothermal method. EDA connects the inorganic units through (N-H center dot center dot center dot O-Ge) H-bonding to form a sub-nanometer periodic structure in the nanowires. This structure exhibits an obvious quantum confinement effect and thereby a blue-shift in the UV/vis spectrum. A Fe2O3-assisted growth mechanism is proposed, in which (N-H center dot center dot center dot O-Ge) H-bonding induces anisotropic growth of the nanowires.