A combination of electrostatic force microscopy and optical microscopy was used to investigate the charge state of individual CdSe nanowires upon local illumination with a focused laser beam. The nanowires were found to be positively charged at the excitation spot and negatively charged at the distant end(s). For high laser powers, the amount of accumulated charges increases logarithmically with the laser power. These effects are described by a diffusion-based model where the results are in good agreement with the experimentally observed effects. On the basis of this model the charge imbalance along the nanowire should establish in the course of nanoseconds. The net charge separation within homogeneous nanowires upon local illumination is of importance for several electronic devices.