This paper investigates the augmentation of heat transfer during pool boiling of a novel aqueous binary mixture of surfactants. The surfactants used were sodium dodecyl sulfate (SDS) (anionic), centrimonium bromide (CTAB) (cationic), and nicotine (nonionic). The aqueous binary mixtures SDS–CTAB, CTAB–nicotine, and SDS–nicotine were prepared on the volume percentage basis. A reduction in surface tension was attained by SDS–CTAB, CTAB–nicotine, and SDS–nicotine aqueous mixtures compared to its individual aqueous surfactant solutions at their optimum concentrations. The most significant surface tension result was obtained by the novel SDS–nicotine aqueous binary system at 25:75 volume percentages. The heat transfer augmentation was investigated by studying the single bubble dynamic in the aqueous SDS–nicotine mixture. The investigation was conducted at two values of heat fluxes to probe the effect of heat flux on bubble dynamics. A significant decrement in the bubble departure diameter and a substantial increment in the release frequency was observed for the SDS–nicotine aqueous mixture at both heat fluxes. The heat transfer coefficient was found to be increased by 36.32% and 58.67% compared to saturated water at low and high heat flux, respectively.