2D electron gases (2DEGs) in oxides show great potential for the discovery of new physical phenomena and at the same time hold promise for electronic applications. In this work, angle-resolved photoemission is used to determine the electronic structure of a 2DEG stabilized in the (111)-oriented surface of the strong spin–orbit coupling material KTaO3. The measurements reveal multiple sub-bands that emerge as a consequence of quantum confinement and form a sixfold symmetric Fermi surface. This electronic structure is well reproduced by self-consistent tight-binding supercell calculations. Based on these calculations, the spin and orbital texture of the 2DEG is determined. It is found that the 2DEG Fermi surface is derived from bulk J = 3/2 states and exhibits an unconventional anisotropic Rashba-like lifting of the spin- degeneracy. Spin-momentum locking holds only for high-symmetry directions and a strong out-of-plane spin component renders the spin texture threefold symmetric. It is found that the average spin-splitting on the Fermi surface is an order of magnitude larger than in SrTiO3, which should translate into an enhancement in the spin–orbitronic response of (111)-KTaO3 2DEG- based devices.