Bismuth telluride (Bi2Te3) is a well-known thermoelectric material with potential applications in several different emerging technologies. The bulk structure is composed of stacks of quintuple sheets (with weak interactions between neighboring sheets), and the performance of the material can be significantly enhanced if exfoliated into two-dimensional nanosheets. In this study, eight different imidazolium-based ionic liquids are evaluated as solvents for the exfoliation and dispersion of Bi2Te3 at temperatures ranging from 350 to 550 K. Three distinct exfoliation mechanisms are evaluated (pulling, shearing, and peeling) using steered molecular dynamics simulations, and we predict that the peeling mechanism is thermodynamically the most favorable route. Furthermore, the [Tf2N-]-based ionic liquids are particularly effective at enhancing the exfoliation, and this performance can be correlated to the unique molecular-level solvation structures developed at the Bi2Te3 surfaces. This information helps provide insight into the molecular origins of exfoliation and solvation involving Bi2Te3 (and possibly other layered chalcogenide materials) and ionic liquid solvents.