With the advancement of large-scale coal development and utilization, low-rank coal (LRC) is increasingly gaining prominence in the energy sector. Upgrading and ash reduction are key to the clean utilization of LRC. Flotation technology based on gas/liquid/solid interfacial interactions remains an effective way to recover combustible materials and realize the clean utilization of coal. The traditional collector, kerosene, has demonstrated its inefficiency and environmental toxicity in the flotation of LRC. In this study, four eco-friendly tetrahydrofuran ester compounds (THF-series) were investigated as novel collectors to improve the flotation performance of LRC. The flotation results showed that THF-series collectors were more effective than kerosene in enhancing the LRC flotation. Among these, tetrahydrofurfuryl butyrate (THFB) exhibited the best performance, with combustible material recovery and flotation perfection factors 79.79% and 15.05% higher than those of kerosene, respectively, at a dosage of 1.2 kg/t. Characterization results indicated that THF-series collectors rapidly adsorbed onto the LRC surface via hydrogen bonding, resulting in stronger hydrophobicity and higher electronegativity. High-speed camera and particle image velocimeter (PIV) observation further demonstrated that THFB dispersed more evenly in the flotation system, reducing the lateral movement of bubbles during their ascent, lowering the impact of bubble wakes on coal particles, and promoting the stable adhesion of bubbles to the LRC surface within a shorter time (16.65 ms), thereby preventing entrainment effects. This study provides new insights and options for the green and efficient flotation of LRC.