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Photochemical vapor generation (PVG) of germanium (Ge) was first reported in this work. The synergistic effect from cobalt/chloride ions and air-liquid interfaces was found for the PVG of Ge. No obvious signal response was observed from the standard solution of Ge in 10% (v/v) formic acids (FAs) under UV irradiation. The addition of 300 mg L−1 of Co2+ and 30 mmol L−1 of Cl− resulted in enhanced photochemical reduction for Ge, and the introduction of air-liquid interfaces proceeding and succeeding the sample solution caused another 4.6 folds of enhancement in signal response of Ge. Under the selected condition, the limit of detection (LOD, 3σ, n = 11) was obtained to be 0.008 ng mL−1 with inductively coupled plasma mass spectrometry (ICP MS) measurement. A good precision, expressed as a relative standard deviation (RSD, n = 7) of 2.0%, was found from replicated measurements of 2 ng mL−1 of Ge. The generation efficiency was found to be no better than 9 ± 2%. The PVG mechanism of Ge was investigated in this work. The new finding is useful for understanding the principle of PVG, and further exploring the analytical and environmental application of PVG. [ABSTRACT FROM AUTHOR]