The catalytic activity of pyrolysis chars from bio-waste was investigated for the cracking of model tar compounds (ethylbenzene and benzene). Two pyrolysis chars were produced at 700 °C from (1) used wood pallets (UWP), and (2) a 50/50 dry% mixture of food waste (FW) and coagulation-flocculation sludge (CFS). Steam activation at 850 °C was used to study the influence of the porous structure. While coke deposition is known to be responsible for the deactivation of carbonaceous chars and metal catalysts during tar cracking reactions, the deactivation of complex materials such as bio-waste chars has scarcely been studied. For this reason, special attention was paid on the relationships between the physicochemical properties of the chars, the operating conditions, and the deactivation mechanisms. To this aim, the cracking tests were performed over a wide temperature range: 400–650 °C for the ethylbenzene cracking, and 850–950 °C for benzene cracking. After the ethylbenzene cracking tests at 650 °C, the characterisations performed with SEM, BET, FTIR and Raman revealed that coke deposition was responsible for the char’s deactivation. The high specific surface area of activated chars explained their higher catalytic activity, and mesoporous catalysts were proved to be more resistant to coke deactivation than microporous catalysts. For these reasons, the higher ethylbenzene conversion (85.8%) was reached with the activated char from food waste and sludge (ac.FW/CFS). For benzene cracking at higher temperature (850 and 950 °C), the chars from food waste and sludge (FW/CFS) were the most active catalysts, despite their deactivation by the melting, diffusion and sintering of the inorganic species. This original deactivation mechanism, reported for the first time, led to the formation of an inorganic layer composed of P and Ca species at the char surface, with some areas rich in KCl and NaCl. Non-activated char from food waste and sludge (c.FW/CFS) was surprisingly proved to be more resistant to deactivation by inorganic species than the activated char (ac.FW/CFS) during the benzene cracking tests at 950 °C. This extended catalytic activity was explained by the activation of the non-activated char (c.FW/CFS) with the CO2 contained in the syngas which simultaneously developed the porosity and created new available active sites. This study marks a step forward in the understanding of the relationships between the deactivation mechanisms, the physicochemical properties of the chars, and the cracking temperature. Finally, a proposal for process integration is presented to consider the possibility to valorise the chars as catalysts to decompose the tar generated in the same pyro-gasification process.