The straightforward, cost-efficient, and scalable route of preparing graphene oxide-based materials (GOBMs) from graphite and transforming them into thermally reduced graphene oxide-based materials (T-RGOBMs) through heat treatment offers unparalleled versatility in customizing and refining the physicochemical properties of T-RGOBMs for various applications. To fully exploit the potential of this route, it is essential to determine the correlation between the physicochemical properties of the resulting T-RGOBMs and the preparation and heat treatment conditions of GOBMs. This article intends to provide a comprehensive discussion of the use of heat treatment routes to prepare T-RGOBMs with finely tuned physicochemical properties for specific applications. The review will focus on the key factors that can affect the end-product features, including the method of preparation of graphite oxide, the physical form of the ensuing GOBMs, and the parameters of the heat treatment process, such as temperature, heating rate, duration, atmosphere, and pressure. Furthermore, it will concentrate on the thermal transformations that take place during heat treatment, delve into the mechanisms and kinetics governing thermal decomposition, evaluate the potential risks associated with reducing GOBMs through heat treatment, and outline strategies to ensure a safe reduction process. The review will also explore recent advancements in the application of T-RGOBMs, providing examples of heat treatment strategies employed across various fields, including supercapacitors, gas sensing, and interference shielding. It serves as a useful guide for researchers and practitioners looking to appropriately prepare GOBMs and safely utilize the heat treatment to fine-tune their properties toward specific applications.