This paper investigated the agglomerating and wetting behaviour during coal dust suppression via the synergistic application of hydrocarbon and short-chain-fluorocarbon surfactants in the presence of electrolytes. A maximum 51.01% and 53.12% reduction in surface tension is achieved after compounding FS-50 and FS-3100 with SDBS and FMEE. Short-chain fluorocarbon surfactants reduced the immersing time of coal particles from maximum 637.03 s to minimum 28.06 s, and further diminished to 9.33 s in the presence of electrolytes. The addition of short-chain fluorocarbon and electrolytes can significantly promote the agglomeration behaviour among treated coal particles. After the addition of NaCl and NaAc, the maximum dust suppression rate reaches 95.12%, which is 1.21–1.33 times of binary surfactants and 1.59–2.01 times of the solely application of hydrocarbon ones. The agglomerating behaviour is more sufficient in predicting the dust suppression rate. The larger the coal particles, the higher liquid bridge force and stronger agglomerated coal particle clusters.