In the analysis of X-ray fluorescence spectra from planetary surfaces, it is traditionally assumed that the observed surface is a plane-parallel, smooth, and homogeneous medium. The spectral and spatial resolutions of the instruments that have been used to measure X-ray emission from planetary surfaces to date have been such that this has been a reasonable assumption, but a new generation of X-ray spectrometers will provide enhanced spectral and spatial resolutions when compared with previous instrumentation. In light of these improvements in performance, it is important to assess how the requirements on the methodology of analysis of spectra may change when the surface is considered as a regolith. At other wavelengths, varying physical properties of planetary regoliths, such as the packing density, are known to have an effect on the observed signal as a function of viewing geometry. In this paper, the results from laboratory X-ray fluorescence measurements of regolith analogue materials at different viewing geometries are presented. Characteristic properties of the regolith such as particle sizes and packing density are found to affect the measured elemental line ratios. A semiempirical function is introduced as a tool for fitting fluorescent line intensity dependences as a function of viewing geometry. The importance of the results is discussed and recommendations are made for the future analysis of planetary X-ray fluorescence data.