In this paper, tetrahydrofurfuryl-functionalized polystyrene nanoparticles (TFPNs) were evaluated as collectors in low-rank coal flotation. A series of TFPNs were prepared by immobilizing tetrahydrofurfuryl groups onto the surface of polystyrene nanoparticles (PNs), and further characterized in terms of their size, shape, surface charge and surface functionalization group concentration (SFGC). The coal flotation performance using TFPNs was compared to that using PNs and diesel oil (DO). The interaction mechanisms between TFPNs and low-rank coal were also discussed. The results show that TFPNs gave higher recovery than that given by PNs and DO. Smaller TFPNs were more effective flotation collectors. The recovery of TFPNs increased firstly and then decreased with SFGC. TFPNs can specifically deposit onto the low-rank coal particles with the hydrogen bonding function between tetrahydrofurfuryl groups and oxygen-containing functional groups, and promote low-rank coal flotation by increasing the hydrophobicity and roughness of coal particle surface with the adsorbed TFPNs. It was demonstrated that TFPNs introduced a new class of collectors for low rank coal flotation.