Abstract. We report a synchrotron study of GeO₂ nanowires (NWs) prepared by a vapor- liquid-solid (VLS) method on a silica glass substrate. The electronic and local structure of GeO₂ NWs were studied by X-ray Absorption Near-Edge Structure (XANES) at the O K- and Ge L_3,2-edges. X-ray Excited Optical Luminescence (energy and time resolved) were used to monitor the optical emission upon X-ray absorption with the excitation energy tuned across absorption edges of interest. Using this method one obtains site specific insight into the chemical origin of luminescence.