The sustainable utilization of biomass, particularly troublesome waste biomass, has become one of the pathways to meet the urgent demand for providing energy safety and environmental protection. The variety of biomass hinders the design of energy devices and systems, which must be highly efficient and reliable. Along with the technological developments in this field, broad works have been carried out on the mathematical modeling of the processes to support design and optimization for decreasing the environmental impact of energy systems. This paper aims to provide an extensive review of the various approaches proposed in the field of the mathematical modeling of the thermochemical conversion of biomass. The general focus is on pyrolysis and gasification, which are considered among the most beneficial methods for waste biomass utilization. The thermal and flow issues accompanying fuel conversion, with the basic governing equations and closing relationships, are presented with regard to the micro- (single particle) and macro-scale (multi-particle) problems, including different approaches (Eulerian, Lagrangian, and mixed). The data-driven techniques utilizing artificial neural networks and machine learning, gaining increasing interest as complementary to the traditional models, are also presented. The impact of the complexity of the physicochemical processes and the upscaling problem on the variations in the modeling approaches are discussed. The advantages and limitations of the proposed models are indicated. Potential options for further development in this area are outlined. The study shows that efforts towards obtaining reliable predictions of process characteristics while preserving reasonable computational efficiency result in a variety of modeling methods. These contribute to advancing environmentally conscious energy solutions in line with the global sustainability goals.