The Curiosity rover has been characterizing mineralogical and chemical compositions of Gale crater soils on Mars since 2012. Given its sub-millimeter scale of analysis, the ChemCam instrument is well suited to study the composition of soil constituents. However, the interpretation of LIBS data on soils in the martian environment is complicated by the large diversity of particle sizes (from dust to sand), combined with the unknown physical arrangement of their mineral constituents (i.e., the type of grain mixtures). For example, martian soils contain a significant amount of X-ray amorphous materials whose physical form remains unclear. In this study, we reproduced martian soil analyses in the laboratory to understand how the LIBS technique can provide specific insights into the physical and chemical properties of granular soils. For this purpose, different types of samples were studied with various ranges of grain sizes, mimicking two possible mixtures that may occur in martian soils: mechanical mixtures of two populations of grains made of distinct chemical compositions; and material forming a compositionally distinct coating at the surface of grains. Our results, also supported by in situ ChemCam data, demonstrate that both the sizes and the type of mixture of soil particles have a strong influence on the LIBS measurement. For mechanical mixtures of two populations of grains larger than 125–250 μm, the scatter of the data provides information about the chemical composition of the end-members. On the other hand, the chemistry recorded by LIBS for grains with surface coatings is fully dominated by the outer material for grains smaller than 500 μm in diameter. This is due to the small penetration depth of the laser (~0.3–1.5 μm per shot), combined with the ejection of small grains at each shot, which leads to a constant replenishment of fresh material. This experimental work will thus improve our understanding of martian soils analyzed by ChemCam, and more broadly, will benefit LIBS studies of granular materials.