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This paper addressed the effect of copper acetate on the combustion characteristics of anthracite depending on the fractional composition of fuel and additive introduction method. Anthracite was impregnated with 5 wt% of Cu(CH3COO)2 by mechanical mixing and incipient wetness impregnation. Four anthracite samples of different fraction with d < 0.1 mm, d = 0.1-0.5 mm, d = 0.5-1.0 mm, and d = 1.0-2.0 mm were compared. According to EDX mapping, incipient wetness impregnation provides a higher dispersion of the additive and its uniform distribution in the sample. The ignition and combustion characteristics of the modified anthracite samples were studied by thermal analysis and high-speed video recording of the processes in a combustion chamber (at heating medium temperature of 800 °C). It was found that copper acetate increases anthracite reactivity, which was evidenced by decreased onset temperature of combustion (ΔTi) by 35-190 °C and reduced ignition delay time (Δτi) by 2.1-5.4 s. Copper acetate reduces fuel underburning (on average by 70%) in the ash residue of anthracite and decreases the amount of CO and NOx in gas-phase products (on average by 18.5% and 20.8%, respectively). The mechanism for activation of anthracite combustion by copper acetate is proposed.