In X-ray fluorescence (XRF) analysis, physical traceability chains are used to quantify the absolute elemental content in a sample. The physical traceability chain relies on absolute knowledge of the X-ray spectral distribution used for the excitation of the instrument and is currently used at synchrotron radiation facilities. Here, we discuss the transfer of the physical traceability chain to laboratory-based X-ray sources, which are often polychromatic, with the view to generate wider application of quantitative XRF analysis.