We study the band structure of the Bi2Se3 topological insulator (111) surface using angle-resolved photoemission spectroscopy. We examine the situation where two sets of quantized subbands exhibiting different Rashba spin-splitting are created via bending of the conduction (CB) and the valence (VB) bands at the surface. While the CB subbands are strongly Rashba spin-split, the VB subbands do not exhibit clear spin-splitting. We find that CB and VB experience similar band bending magnitudes, which means, a spin-splitting discrepancy due to different surface potential gradients can be excluded. On the other hand, by comparing the experimental band structure to first principles LMTO band structure calculations, we find that the strongly spin-orbit coupled Bi 6p orbitals dominate the orbital character of CB, whereas their admixture to VB is rather small. The spinsplitting discrepancy is, therefore, traced back to the difference in spin-orbit coupling between CB and VB in the respective subbands' regions. 73, The narrow bandgap semiconductor Bi 2 Se 3 has been known for decades for its good thermoelectric properties [1,2]. The recent observation of a topologically protected surface state (TSS) in Bi 2 Se 3 [3, 4] marked the discovery of a model system for 3D topological insulators (TIs) and has lead to a surge of renewed interest in the properties of this material. The Bi 2 Se 3 (111) surface hosts within a gap of bulk bands projected onto the surface Brillouin zone (BZ) a single TSS with Dirac cone dispersion [3][4][5]. Similar TSS dispersion has been found in other Bi-based systems, such as, Bi 2 Te 3 and PbBi 2 Te 4 [4, 6]. The TSS is robust against scattering from non-magnetic perturbations. Moreover, it possesses a helical character, which infers a defined spin polarization for a particular momentum value. These characteristics might lend themselves to a variety of new applications, especially, in spintronics, where transport and manipulation of spin currents at high temperatures and with diminutive scattering interactions are sought out [7][8][9][10].It has already been shown that the modification of the Bi 2 Se 3 surface with non-magnetic adsorbates [4,[11][12][13][14], as well as heating up to 400 K [15] does not alter TSS protection. However, it dopes the TSS and can even change surface electronic properties. Surface n-doping creates two sets of new states at the surface, which appear simultaneously in the immediate vicinity of the TSS within the projected bulk conduction band (CB) and valence band (VB) regions. While parabolic bands with a large Rashba splitting are observed above the Dirac point (E D ), the bands below are M-shaped, can overlap with the TSS, and do not show a clear spin splitting. These two band sets have been mainly interpreted as quantized subbands resulting from the confinement of a pair of two-dimensional electron gases (2DEGs) at the surface created via CB and VB bending [13,14,[16][17][18]. Practically, the largely spin-split bands add a new feature to Bi 2 Se 3 surface for spintron...