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Spin-split Rashba bands have been exploited to efficiently control the spindegree of freedom of moving electrons, which possesses a great potential infrontier applications of designing spintronic devices and processing spin-basedinformation. Given that intrinsic breaking of inversion symmetry and sizeablespin-orbit interaction, two-dimensional (2D) surface alloys formed by heavymetal elements exhibit a pronounced Rashba-type spin splitting of the surfacestates. Here, we have revealed the essential role of atomic orbital symmetry inthe hexagonally warped Rashba spin-split surface state of$\sqrt{3}\times\sqrt{3} R30^{\circ}$ BiCu$_{2}$ monatomic alloy by scanningtunneling spectroscopy (STS) and density functional theory (DFT). From$\mathrm{d}I/\mathrm{d}U$ spectra and calculated band structures, threehole-like Rashba-split bands hybridized from distinct orbital symmetries havebeen identified in the unoccupied energy region. Because of the hexagonallydeformed Fermi surface, quasi-particle interference (QPI) mappings haveresolved scattering channels opened from interband transitions of\textit{p$_{x},$p$_{y}$}($m_{j}=1/2$) band. In contrast to the\textit{s,p$_{z}$}-derived band, the hexagonal warping predominately isaccompanied by substantial out-of-plane spin polarization $S_{z}$ up to 24\% inthe dispersion of \textit{p$_{x}$,p$_{y}$}($m_{j}=1/2$) band with an in-planeorbital symmetry.

Orbital-enhanced Warping Effect in  P\textsubscript{x},P\textsubscript{y}-derived Rashba Spin Splitting of  Monatomic Bismuth Surface Alloy Surface Alloy