Sodium salt additions provide an effective route for tuning the combustion behavior of solid fuels. The salt-fuel surface interactions play a key role in combustion, as demonstrated by low heating rate experiments. High heating rate single particle studies have not investigated the effect of surface interactions and microstructural changes for sodium salt-treated fuels. In this work, the effect of three different sodium salt treatments were investigated on the single particle combustion characteristics of two distinct solid fuels and their corresponding chars. This approach probed the influence of microstructural changes and the formation of oxidation-resistive functional groups during high heating rate combustion. The separate characterization of biomass, coal, and their respective chars aimed at identifying the effect of sodium during different stages of combustion. The investigation encompassed Tunçbilek lignite (TL), olive residue (OR), and their fast pyrolysis chars (TLc and ORc) obtained from a wire mesh reactor at 600 °C. Both pristine and char particles were treated with Na2CO3, NaOH, and NaAlO2 to investigate the catalytic/inhibiting effects at different stages of combustion, namely, ignition, volatile combustion, and char combustion. All samples were burned as single particles at a high heating rate, WMR (1600 °C s−1). Treated OR samples provided earlier ignition reaching ∼ 0.4 s for OR-OH and shorter char combustion times around ∼ 2.8 s mg−1 for OR-CO3. On the contrary, treated TL samples depicted slightly higher ignition delay (3.0 s for TL-OH) and prolonged char combustion (11.2 s mg−1 for TL-OH) compared to TL (2.3 s, 8.2 s mg−1). Treated TLc samples also exhibited higher ignition delay due to the hygroscopic behavior of the sodium salts, which is more pronounced in TLc-OH (5.5 s). All treated chars exhibited shorter char combustion times except TLc-OH. Overall, sodium salt additions improved characteristic combustion times of biomass and chars while inhibiting those of lignites. The inhibitive effect of sodium salts on treated OR and ORc samples was more pronounced for TGA experiments due to the alkali interaction with the lignocellulosic component and a prolonged heating-up period. The findings demonstrate the importance of high heating rate characterization to accurately understand the sodium salt additions on combustion performance.