X‐ray fluorescence (XRF) is a well‐established nondestructive analytical technique that allows for the characterization of the chemical contents of the specimen examined. Furthermore, it can be made portable and therefore usable for samples that cannot be brought to the laboratory. Despite its great versatility, characterizing samples from the standpoint of elemental content becomes challenging when dealing with complex and irregular structures. In such cases, analytical quantification algorithms struggle, sometimes yielding unreliable results. An alternative to these algorithms is provided by Monte Carlo algorithms, which enable simulation with a level of detail surpassing that achievable with analytical algorithms. They encompass the entire experiment, including the sample's structure and composition. However, the time required to obtain accurate quantification, typically much longer than the measurement time, may pose an insurmountable limit to their practical use. This work will describe and discuss the use of Monte Carlo algorithms for XRF analysis, their performance, and their limitations.