In contradiction to the nature of the spin-orbit driven Rashba splitting of surface states which increases with atomic number, Shikin et al. [Phys. Rev. Lett. 100, 057601 (2008)] have observed that the size of the splitting in Au overlayers on W(110) is smaller than for Ag overlayers. In the framework of first-principle density functional theory, we have studied the origin of the Rashba splitting at Au/Ag overlayers on the W(110) surface. We show how the asymmetric behavior of the wave function in the vicinity of the surface atom nucleus, in addition to the strength of the nuclear potential gradient, plays a crucial role for the size of the splitting. The influence of the electronic structure and spin dependent hybridization on the Rashba splitting is discussed. The asymmetric behavior of the surface wave function originates from the surface-interface sp-d hybridization. We find that a spin dependent hybridization in the Ag overlayer influences strongly the size of the Rashba splitting.The generation of a dissipationless spin current in a twodimensional (2D) electron gas without applying an external field can be achieved by exploiting the spin-orbit coupling (SOC) at surfaces and interfaces. Due to the breaking of the spatial inversion symmetry, surface electrons are subject to an electric field perpendicular to the surface, thereby experiencing an effective magnetic field. The coupling of such a magnetic field to the electron spin causes a k-dependent spin splitting of the surface state known as the Rashba (RB) effect. 1 It was exploited in the concept of spin field effect transistor. 2 This effect was observed first by LaShell et al. for the Shockley surface state of Au(111) 3 and has been extended to several surfaces. [4][5][6][7][8][9][10][11] The SOC Hamiltonian can be divided into two terms according to the momentum components, parallel (k ) and perpendicular (k ⊥ ) to the surface. The k part leads to the RB term H R , while the k ⊥ should be irrelevant for the spin splitting behavior of the in-plane 2D band structure. The RB Hamiltonian iswhereẑ is the surface normal direction, s is the direction of the spin, and α is the RB parameter. The RB energy can be calculated from the integral of the potential gradient along the surface normal direction times the surface wave function squared 12 :Many experimental studies show a large RB splitting due to the SOC at metal surfaces. For example, a large RB splitting was observed for the surface state of hydrogen as well as lithium terminated W(110), bare Bi(100), Au(111), Sb(111), 3,13-16 and also for surface binary alloys like Bi/Ag(111), Pb/Ag(111), and Au/Ge(111). [17][18][19] Since the strength of SOC in a 2D electron gas depends on the atomic number and the potential gradient, it is logical to tailor the size of the splitting by replacing light elements with a mixture of light and heavy elements. 20-22 Such hybrid structure could have potential applications in spintronics devices. It has been observed that the RB splitting of the W(110) surface is enhanced when ...