Abstract: Efficient flotation recovery of fine−grained molybdenite (MoS₂) represents a critical challenge for the sustainable exploitation of molybdenum resources. This review focuses on collector innovation, systematically summarizing recent advances from experimental screening to computational modeling. At the experimental level, nanoemulsions and composite collectors have significantly enhanced the recovery of fine particles by size effects and synergistic adsorption mechanisms. At the computational modeling level, density functional theory (DFT) and molecular dynamics (MD) simulations have elucidated the interfacial interaction mechanisms between collectors and mineral surfaces, facilitating a paradigm shift from "empirical trial−and−error" to "rational design." Emerging collector systems have demonstrated substantial improvements in recovery during industrial tests. Future research must address bottlenecks such as multiscale simulation accuracy and cost−effective green reagent development to advance molybdenum resource processing toward high−efficiency and low−carbon practices.