Fine bubbles with a diameter less than 1 mm are widely used to intensify the gas–liquid processes since the micro-interface they build can significantly improve the mass transfer of gases to the liquid phase. In this study, a coupled mathematical model of motion and mass transfer of a single fine bubble with multicomponent was established and verified for carbon dioxide desorption. The rising and dissolution behaviors of a single fine bubble with different external pressures and initial diameters were observed using a high-speed imaging technique to evaluate the increasing velocity, Vb, and the mass transfer coefficient, kL. Design indicators such as effective mass transfer height and residence stay time of the bubble have been established to guide the optical selection of initial bubble size and liquid level height (reactor height) for a bubbling reactor's optimal design and operation. The comparison between the theoretical calculations and the experimental results proves that the new model can well describe the movement and multicomponent mass transfer behavior of a single fine bubble in an aqueous solution, and the relative errors are less than 5%.