The bound state of a 3He atom at the interface between coexisting crystalline and superfluid phases of 4He is studied theoretically by means of first principle Quantum Monte Carlo simulations. We consider both the case of a solid/superfluid 4He interface, as well as that of a few solid layers of 4He forming on an attractive substrate. It is observed that the 3He bound state is sharply localized in a well-defined, quasi-2D layer of 4He in the region intermediate between the solid and the liquid. The layer in which the 3He atom resides displays an intriguing interplay of atomic localization and quantum-mechanical exchanges; is not necessarily the first “non-solid” layer, as suggested in previous studies, and it is affected by the attractive strength of the substrate.