The application of an external magnetic field can lift the spin degeneracy of electronic states through its interaction with the electronic magnetic moment. A closely-related phenomenon is the Rashba-Bychkov (RB) effect where symmetry breaking at surfaces or interfaces gives rise to an electric field which is in turn seen as an effective magnetic field in the electrons' rest frame. The resulting k-dependent energy splitting of spin-polarized electronic states has been observed on various metal surfaces but the effect is much larger in artificially-grown surface alloys; such as the BiAg2 grown at the surface of Ag(111). The spin splitting magnitude observed in these systems might be very useful in spintronics applications since it could decrease the spin precession time in a spin transistor and distinguish between the extrinsic and intrinsic spin Hall effects. Nevertheless, their metallic character poses serious obstacles in the exploitation of the RB effect due to the presence of spin-degenerate electronic states at the Fermi level which would dominate transport experiments. We have used angle-resolved photoelectron spectroscopy (ARPES) to explore the RB effects on various artificially grown structures, formed on semiconducting substrates. The interplay of quantum confinement and giant RB splitting on a trilayer Si(111)-Ag-BiAg2 system reveals the formation of a complex spin-dependent structure, which can be externally tuned by varying the Ag layer thickness. This provides a means to tailor the electronic structure and spin polarization near the Fermi level, with potential applications on Si-compatible spintronic devices. Moreover, we have discovered a giant spin splitting in a true semiconducting system, namely the Si(111)-Bi trimer phase. The size of the RB parameters is comparable to those of metallic surface alloys. Using theoretical models we have identified the peculiar band topology as the origin of the giant spin splitting on the Bi/Si(111) system. All our findings are supported by relativistic first-principles calculations. Finally, a chapter of this thesis manuscript is devoted to the description of phenomeno-logical theoretical simulation, which can capture the experimental results related to the RB effect on low-dimensional systems. A parallel experimental project is discussed in a separate chapter. It has been focused on the band topology of the novel p(2 × 2) reconstruction of the Pt(111)-Ag-Bi trilayer. We investigated the symmetry properties of the interface states by varying the amount of Ag. ARPES results present the electronic signature of a strain-related structural transition.