We demonstrate the formation of a two-dimensional electron gas (2DEG) at the (100) surface of the 5d transition-metal oxide KTaO3. From angle-resolved photoemission, we find that quantum confinement lifts the orbital degeneracy of the bulk band structure and leads to a 2DEG composed of ladders of subband states of both light and heavy carriers. Despite the strong spin-orbit coupling, our measurements provide a direct upper bound for the potential Rashba spin splitting of only Δk∥∼0.02  Å−1 at the Fermi level. The polar nature of the KTaO3(100) surface appears to help mediate the formation of the 2DEG as compared to nonpolar SrTiO3(100).