It is critical to separate carbon from fly ash due to its increasing amount being produced per year and component requirements for secondary utilizations. Flotation is an efficient technique to fulfill this task. Effects of diesel emulsification using sodium petroleum sulfonate on unburned carbon flotation from a fly ash sample were studied. Flotation tests showed that carbon recovery was increased from 41% to 86% using the emulsified collector at the same dosage level (0.5 kg/ton) as diesel. Zeta potential measurements indicated that both the carbon and emulsified collector droplets carried negative charges within the studied pH range. For fly ash particles with high carbon content, adsorption bands of carbonyl bond (CO) were detected in the FTIR spectra, which agreed with the XPS characterization findings. XPS analysis indicated that the emulsified diesel (ED) collector interacted more intensively with the surface carbon-oxygen groups relative to the normal diesel collector. Finally, the improved efficiency of ED is proved to be related to its polar groups and reduced oil droplet size. The polar groups of ED (mainly sulfonate) interacted with the surface oxygen containing groups (e.g., CO and COOH) through hydrogen bonding and Lewis acid base interaction.