Liquid chromatography-hydride generation-inductively coupled plasma optical emission spectroscopy (LC-HG-ICP/OES) has been used to determine inorganic and organometallic species of germanium. In recent studies these coupled systems has been applied successfully to the speciation of arsenic. To establish separation conditions for germanium two reversed stationary phases and different solvent mixtures for elution, in isocratic or gradient mode have been tested. The reduction of germanium species to the corresponding volatile hydride is a critical step, especially for acidity control, thus the conditions for reduction using different concentrations of acid have been studied systematically. For the conditions established quality parameters as limit of detection (at the μg l−1 level), precision and recovery have been determined for the germanium species considered in a saline matrix.