Abstract: The determination methods of vanadium in geochemical samples include atomic absorption spectrometry, plasma emission spectrometry(ICP-AES), inductively coupled plasma mass spectrometry(ICP-MS), and X-ray fluorescence spectrometry. Four national standard samples were used to determine the content of samples, and the detection limits, accuracy, precision and recovery rates were compared. By comparison, the measured values of the four methods are basically in agreement with the recommended values. The plasma emission spectrometric method has a low detection limit, a wider linear range, a better accuracy and precision, and is more suitable for testing vanadium batches in geochemical samples.