Spin-dependent charge transmission or the so-called chirality-induced spin selectivity (CISS) effect was demonstrated in self-assembled chiral coordinated monolayers. Distinct from the previous CISS phenomenon observed mainly on pure biomolecules, here we expanded this effect to the coordinated complex of chiral biomolecules and metal cations, specifically, cysteine-Cu2+-alanine (Cys/Cu/Ala), in which the complex itself was redox-active. However, the coordinated self-assembled monolayers of cysteine-Cu2+-cysteine did not show any spin-dependent effect. In addition, this phenomenon was explained by developing a theoretical model with spin-orbit coupling. The alanine molecules contributed to multiple transport pathways, leading to experimentally observable spin polarization. Finally, this CISS effect in Cys/Cu/Ala complex was demonstrated to amplify the sensing signal. The enantioselective discrimination efficiency could be improved by controlling the orientation of the external magnetic field.