Over the past years, pyrolysis models have moved from thermal models to comprehensive models with great flexibility including multi-step decomposition reactions. However, the downside is the need for a complete set of input data such as the material properties and the parameters related to the decomposition kinetics. Some of the parameters are not directly measurable or are difficult to determine and they carry a certain degree of uncertainty at high temperatures especially for materials that can melt, shrink, or swell. One can obtain input parameters by searching through the literature; however, certain materials may have the same nomenclature but the material properties may vary depending on the manufacturer, thereby inducing uncertainties in the model. Modelers have resorted to the use of optimization techniques such as gradient-based and direct search methods to estimate input parameters from experimental bench-scale data. As an integral part of the model, a sensitivity study allows to identify the role of each input parameter on the outputs. This work presents an overview of pyrolysis modeling, sensitivity analysis, and optimization techniques used to predict the fire behavior of combustible solids when exposed to an external heat flux.