Today, energy use is an important and urgent issue for economic development worldwide. It is expected that raw material in the form of biomass and lignocellulosic residues will become increasingly significant sources of sustainable energy in the future because they contain components such as cellulose, hemicellulose, lignin, and extractables with high energy-producing potential. It is then essential to determine the behavior of these materials during thermal degradation processes, such as pyrolysis (total or partial absence of air/oxygen). Pyrolyzed biomass and its residual fractions can be processed to produce important chemical products, such as hydrogen gas (H2). Thermogravimetric (TGA) analysis and its derivative, DTG, are analytical techniques used to determine weight loss as a function of temperature or time and associate changes with certain degradation and mass conversion processes in order to evaluate kinetic properties. Applying kinetic methods (mathematical models) to degradation processes permits obtaining several useful parameters for predicting the behavior of biomass during pyrolysis. Current differential (Friedman) and integral (Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose, Starink, Popescu) models vary in their range of heating speeds (β) and degree of advance (α), but some (e.g., Kissinger’s) do not consider the behavior of α. This article analyzes the results of numerous kinetic studies using pyrolysis and based on thermogravimetric processes involving over 20 distinct biomasses. The main goal of those studies was to generate products with high added value, such as bio-char, methane, hydrogen, and biodiesel. This broad review identifies models and determines the potential of lignocellulosic materials for generating bioenergy cleanly and sustainably.