We suggest a unimer-assisted exfoliation method for the exfoliation of van der Waals two-dimensional (2D) materials such as graphene, MoS2, and h-BN and show that the micellar size is a critical parameter for enhancing the exfoliation efficiency. To explain the effectiveness of the unimers in the exfoliation, the influence of the micellar size of a biocompatible block copolymer, Pluronic F-68, is evaluated in view of the yield and thickness of exfoliated 2D flakes. By the addition of water-soluble alcohols, the surfactants exist in the form of a unimer, which facilitates the intercalation into the layered materials and their exfoliation. The results showed that the high exfoliation efficiency could be achieved by controlling the micellar size mostly to be unimers; the average yield rate of MoS2 exfoliation was 4.51% per hour, and the very high concentration of 1.45 mg/mL was obtained by sonication for 3 h. We also suggested the dielectrophoresis technique as a method for forming a film composed of 2D flakes for diverse applications requiring electrical signals. The unimer-assisted exfoliation method will be substantially utilized to achieve highly concentrated aqueous dispersion solutions of 2D materials.