Low rank coal has the characteristics of low coalification degree, high volatile matter, and dense pores; therefore, it has problems such as high reagent consumption and high flotation difficulty. This study investigates the effects and mechanisms of surfactant-enhanced Fischer-Tropsch synthesis intermediates (FTI) on the flotation of low-rank coal using a combination of experimental analysis and molecular simulations. When FTI was mixed with 5% surfactant, the collector exhibited improved flotation performance. Three flotation collectors were prepared by blending Span80 and Tween80 with FTI: SFTI-EM (emulsification treatment with Span80 and FTI), SFTI-CO (compound treatment with Span80 and FTI), and TFTI-EM (emulsification treatment with Tween80 and FTI). Flotation test results showed that SFTI-EM and SFTI-CO demonstrated outstanding flotation performance, increasing clean coal yield by 50% compared with diesel collectors. Under identical dosage conditions, SFTI-CO achieved approximately 5% higher clean coal yield than SFTI-EM, while SFTI-EM reduced FTI consumption by about 40%, indicating higher economic value. Molecular dynamics simulations revealed that Span80 molecules adsorbed more firmly on low-rank coal surfaces than Tween80, forming a “bridging” effect between hydrocarbon oil and coal surfaces, thereby enhancing hydrocarbon adsorption on coal. Additionally, the SFTI-EM emulsion exhibited an “oil-water-oil” multiphase droplet structure, facilitating reagent-coal contact. Contact angle measurements further suggested that surfactants contribute to forming more stable mineralized froth, further improving flotation efficiency. This study has not only developed a high-efficiency and economical flotation collector alternative to diesel, but also demonstrated the enhancing effect of non-ionic surfactants combined with FTI on low-rank coal flotation.