In this chapter, the synergistic mechanism and the resulting influence during co-pyrolysis of coal and biomass, are summarized. The properties of coal and biomass, the release and migration of alkali and alkaline earth metals (AAEMs), the interaction between volatile and char, the characteristics of the resulting volatiles, and the physicochemical structure and reactivity of co-pyrolysis char, are also analyzed. In addition, the influence of AAEMs on the properties of the co-pyrolysis products is reviewed. Moreover, the analysis of the co-pyrolysis industry demonstration is also mentioned. Finally, this chapter also proposes some additional possibilities, based on further literature research.