Slag formation in the grate-kiln process is a major problem for iron-ore pellet producers. It is therefore important to understand the slag formation mechanism in the grate-kiln production plant. This study initiated the investigation by in situ sampling and identifying particles in the flue gas from a full-scale 40 MW grate-kiln production plant for iron-ore pelletizing. Particles were sampled from two cases of combustion with pulverized coal and heavy fuel oil. The sampling location was at the transfer chute that was situated between the traveling grate and the rotary kiln. The particle-sampling system was set up with a water-cooled particle probe equipped with nitrogen gas dilution, cyclone, and low-pressure impactor. Sub-micrometer and fine particles were size-segregated in the impactor, while coarse particles (>6 μm) were separated with a cyclone before the impactor. Characterization of these particles was carried out with environmental scanning electron microscopy (ESEM), and the morphology of sub-micrometer particles was studied with transmission electron microscopy (TEM). The results showed that particles in the flue gas consisted principally of fragments from iron-ore pellets and secondarily of ashes from pulverized coal and heavy fuel oil combustions. Three categories of particle modes were identified: (1) sub-micrometer mode, (2) first fragmentation mode, and (3) second fragmentation mode. The sub-micrometer mode consisted of vaporized and condensed species; relatively high concentrations of Na and K were observed for both combustion cases, with higher concentrations of Cl and S from heavy fuel oil combustion but higher concentrations of Si and Fe and minor P, Ca, and Al from coal combustion. The first fragmentation mode consisted of both iron-ore pellet fines and fly ash particles; a significant increment of Fe (>65 wt %) was observed, with higher concentrations of Ca and Si during heavy fuel oil combustion but higher concentrations of Si and Al during coal combustion. The second fragmentation mode consisted almost entirely of coarse iron-ore pellet fines, predominantly of Fe (∼90 wt %). The particles in the flue gas were dominantly iron-ore fines because the second fragmentation mode contributed >96 wt % of the total mass of collected particles.