Engineering high valley degeneracy is a common design strategy for achieving high thermoelectric performance, as it enables high electrical conductivity while simultaneously maintaining high thermopower. In the absence of intervalley scattering, the thermoelectric quality factor, which determines the maximum thermoelectric figure of merit zT , is directly proportional to the valley degeneracy N V . Improving zT by increasing the valley degeneracy has been a focus of many studies; for example, converging the valence bands of PbTe at the L-point (N V = 4) and along the Σ-line (N V = 12) has been shown to improve the thermoelectric performance of p-type PbTe. Recently, nontrivial electronic structure topologies have also attracted interest as a strategy for increasing the valley degeneracy in materials such as rock-salt SnSe, PbTe-SnTe-GeTe alloys, and Bi 2 Te 3 . In these systems, it is often discussed that band inversion leads to highly-corrugated Fermi surfaces with multiple carrier pockets near the band edge. It is curious however that band inversion leads to high valley degeneracy in some materials while it does not in others; for example, Bi 2 Te 3 has inverted bands and exhibits high valley degeneracy (N V = 6), whereas the chemically similar Bi 2 Se 3 also has inverted bands but exhibits a single carrier pocket at the Γ-point (N V = 1). While band inversion is a key characteristic of topological insulators in the context of surface/edge states, comparatively little is discussed regarding the consequent electronic structure in the bulk.