After montmorillonite (MTM) was first exfoliated into nanosheets as a reinforcing filler in the 1980s, layered clay became a hotspot of interest. However, to date, the exfoliation of the resource-rich and inexpensive layered MTM into high-quality nanosheets still remains a significant challenge. Herein, a simple and effective strategy to exfoliate layered MTM into mono-layered sheets via the aggregation of polyethyl-phosphate glycol ester (Exolit OP 550) is proposed. A significant decrease in exfoliation time from 120 min to 3 min was observed at room temperature only via a gentle stirring process. Moreover, various factors that reduce the viscosity of the mixture could be utilized to boost the exfoliated concentration to a record high value of 100 wt%, which is an increase of 460-2400% compared with that in other works. A tentative model was also proposed to illustrate the exfoliation mechanism based on the detection of segmental confined movement, structural evolution, and polymer-clay interaction. Particularly, the as-observed critical concentration of 200 wt% MTM indicated a saturation effect for the surface-adsorbed polymer. The critical concentration for the onset of exfoliation was 150 wt%. In addition, the structure of the exfoliated nanosheets in Exolit OP 550 underwent a temperature-sensitive and irreversible transformation. Thus, our study may provide new insight for the exfoliation of clay.