A calibration method for proposed x-ray fluorescence (XRF) measurements of arsenic and selenium in nail clippings is demonstrated. Phantom nail clippings were produced from a whole nail phantom (0.7 mm thickness, 25 × 25 mm(2) area) and contained equal concentrations of arsenic and selenium ranging from 0 to 20 µg g(-1) in increments of 5 µg g(-1). The phantom nail clippings were then grouped in samples of five different masses: 20, 40, 60, 80 and 100 mg for each concentration. Experimental x-ray spectra were acquired for each of the sample masses using a portable x-ray tube and a detector unit. Calibration lines (XRF signal in a number of counts versus stoichiometric elemental concentration) were produced for each of the two elements. A semi-empirical relationship between the mass of the nail phantoms (m) and the slope of the calibration line (s) was determined separately for arsenic and selenium. Using this calibration method, one can estimate elemental concentrations and their uncertainties from the XRF spectra of human nail clippings.