A simple procedure is proposed to determine the total reflection X-ray fluorescence (TXRF) spectrometer sensitivity curve; this procedure provides better accuracy and exactitude than the standard established method. It uses individual pure substances instead of the use of vendor-certified values of reference calibration standards, which are expensive and lack any method to check their quality. This method avoids problems like uncertainties in the determination of the sensitivity curve according to different standards. It also avoids the need for validation studies between different techniques, in order to assure the quality of their TXRF results.