Abstract: A method for determination of 14 elements, including silicon, manganese, phosphorus, sulfur, nickel, chromium, vanadium, molybdenum, copper, titanium, tungsten, arsenic, tin, and lead in pig iron samples by wavelength dispersive X-ray fluorescence spectrometry was proposed. The pig iron sample (35 mm of diameter and 8 mm of thickness) was obtained with Heraeus hot metal sampler, knocked out immediately under red heat condition and rapidly cooled in a cold water tank, and then polished with a particle size of 0.25 mm sandpaper. Spectral line overlap interference was corrected by the built-in digital regression method of the instrument, and calibration curves were drawn with pig iron standard samples and internal control samples. As shown by the results, the detection limits of the elements were in the range of 0.000 3%—0.001 4%. RSDs (n=10) of the determined values of test of sample for precision were less than 2.5%. This method was used to analyze 3 actual pig iron samples, and the determination results of 14 elements were basically consistent with those by the corresponding national standard methods.