Coal combustion and mineral particle heating experiments were carried out in a drop-tube furnace at 1373 and 1573 K, respectively, to investigate the temperature effect on central-mode particulate matter (PM) formation during the combustion of coals with different mineral compositions. Two bituminous coals, coal A and coal B, with similar organic properties but different Ca/Fe mineral contents were tested. Typical minerals in the two coals, calcite and kaolinite, were used in the mineral particle heating experiments. An air atmosphere, a sample-feeding rate of 0.3 g/min, and a particle residence time of about 2 s were adopted in these experiments. The PM and bulk ash samples were collected by a low-pressure impactor and fiber filters, respectively, through a water-cooled N-2-quenched probe. The elemental compositions, mass concentrations of PMs, mineral compositions, and morphologies of bulk ashes were characterized. The results show that the mass fraction size distribution of aluminum (Al) can be used to identify the different PM formation modes. When the temperature is increased from 1373 to 1573 K, the central-mode PM concentration for coal A increases by 61.8%, whereas that for coal B decreases by 13.2%. The remarkable difference is attributed to different fragmentation and coalescence behaviors resulting from different mineral compositions of the two coals. The criteria of optimal coal mineral composition for melting-phase generation and coalescence occurrence are developed. Interactions between calcite and kaolinite and their influence on central-mode particle formation with respect to the temperature are clarified by the mineral particle heating experiments.