A biofilm, a community of microorganisms, is highly resistant to antibiotics, resulting in massive losses in various areas. We herein present a strategy to remove Streptococcus mutans biofilms through a spontaneous exfoliation by the synergistic effect between zwitterion and sugar alcohols. It is assumed that the anionic site of zwitterion can be coupled with sugar alcohols and the cationic site remains in the state of lacking electrons. The cationic site allows the complexes to be delivered to negatively charged exopolysaccharides of biofilms. This strategy facilitates a significant increase in the ability of sugar alcohols to disperse aggregated exopolysaccharides. In this work, it was demonstrated that the mixture of betaine and erythritol existed as a complex in water and that the complex induced a spontaneous detachment of biofilms from the surface to which the biofilms had been adhered. This detachment resulted from a reduction in adhesive forces of the biofilms due to an increase in solubility of bacterial exopolysaccharides. The effects triggered by the formation of complex between zwitterion and sugar alcohol provide a simple and safe way to remove biofilms without antibiotics and physical forces.