Since more than a decade ago, the topic of multilayer thin film analysis using Fundamental Parameters (FP) method has been addressed by many authors. However, as a general approach to the implementation of this method, an iteration must be applied directly with the theoretical equations. In many cases, this procedure can become very time-consuming and sometimes cause divergence problems, especially when a complicated layer structure is involved or some special requirement for the analysis must be satisfied. In this work we adopted a new approach to the analysis of some types of multilayer thin films, which is conceptually similar to die well known theoretical alphas method used in bulk sample analysis in the sense that they all use FP theoretical calculations to establish mathematical relationships between the XRF intensity and the quantities of interest.