The motivation for this review is the need to understand the interdependence of porous structure and reactivity of highly porous carbonaceous materials during oxidation. These materials can be oxidized in three regimes: regime I, kinetically controlled conditions; regime II, partial diffusion-controlled conditions; regime III, diffusion controlled conditions. Since the emphasis here is on the porous structure and its influence on reactivity, conditions where transport processes are dominant were not included for they mask the view of interest. Therefore, the review discusses only physicochemical processes occurring during oxidation of highly porous chars in regime I. Furthermore, reactivity is influenced by many factors, such as catalysis, volatile matter, and water content. To avoid the effect of these factors, highly porous synthetic chars with nothing but elemental carbon and residual hydrogen and oxygen was chosen. Mainly, we discuss a commercial product known as Spherocarb which consists of spherica l particles with specific surface area of about 1000 m2 g-1 and porosity of about 0.6. These particles are well defined and reproducible in their properties. They serve well as model materials for various synthetic chars, coal chars, and other carbonaceous materials. The review presents in a systematic manner macroscopic properties and processes that shed light on different aspects of porosity and reactivity. These are presented both from experimental observation as well as modeling view. An attempt was made to present a porous structure model that can reconstruct all available experimental data on these particles during oxidation. In the review the following processes and properties are discussed: shrinkage, fragmentation, and porosity. All are directly connected to porous structure and reactivity.