Abstract: The glassy melt of the ferrovanadium sample for XRFS analysis was prepared and auto-shaped by fusion with lithium tetraborate and lithium metaphosphate in a Pt-Au crucible. Major element(Ⅴ) and minor elements (i.e., Si, Mn, Al, P) were determined by XRFS. The optimum mass ratio among lithium tetraborate mixed flux (lithium tetraborate+lithium metaphosphate=67+33) and sample was found to be 30 to 5 to 1. Values of detection limit found were in the range of 12.4-51.2 μg·g-1. The proposed method was used in the analysis of CRM′s, giving results in consistency with the certified values.