Uniform chain-like GeO₂–Zn₂GeO₄ nanostructures were fabricated in a high yield by a vapor-phase reaction of Ge vapor and Zn vapor in a tube furnace system. In this structure, numerous GeO₂ nanobeads attached the long Zn₂GeO₄ nanowires to form the hybrid GeO₂–Zn₂GeO₄ nanochains. The formation process, structure and morphology of these chain-like structures are investigated carefully. A strong green emission was observed when the sample was irradiated with a 254 nm UV lamp. In addition, by annealing the sample in the reduced atmospheres, we are able to tune the emission color of the products from green to blue-white. Moreover, long lasting luminescence from these nanochains was also observed. Their hybrid structures clearly contribute to their interesting optical properties.