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New biofuel raw materials for energy pellet production are now being studied as potential energy sources for the heating market. Because of the complexity of the chemical and physical properties of novel fuels, such as some agricultural residues and energy crops, the study of their ash-related aspects is crucial for the sustainable development of this potential energy sector. Ash fractions formed during fixed-bed combustion of different pelletized novel crops; i.e., two Mediterranean crops (one herbaceous, brassica, and one woody species, poplar) and three Chinese cassava stems (cassava species from three different Chinese regions), and three Chinese cassava stems (cassava species from three different Chinese regions), were characterized, and their formation paths assessed in this study. Special emphasis was placed on elucidating the role of major ash-forming elements in the fractionation and transformation behavior, leading to the formation of bottom ash, deposits, and particulate emissions (fine and coarse ash particle fractions) on the basis of experimental data. In the Mediterranean fuels, the predominant ash fraction obtained was bottom ash, mainly characterized by silicates. Phosphates were found to be the main crystalline phases in the Chinese fuels. The slagging tendency was low for all of the fuels, although more significant for the cassava species under the studied conditions. Further, combustion of the studied Chinese energy crops resulted in a considerably finer particle fraction compared to the Mediterranean fuels. Deposits and particulate matter were dominated by K-sulfates as well as K-chloride in all fuels (except poplar), with the occurrence of K-phosphates for cassava pellets. Overall, this study showed fundamental differences in ash transformation behavior during combustion of P-rich fuels (i.e., cassava mixtures) compared to Si-rich fuels (i.e., poplar and brassica mixtures). Of major importance is the experimental verification of the higher thermodynamic stability of phosphates in relation to silicates. Furthermore, in P-rich fuels at high (K + Na)/(Ca + Mg) ratios, a significant degree of alkali metal volatilization occurs, which forms larger amounts of particulate matter, whereas this ratio has no/low effect in Si-rich fuels at high alkali metal ratios.