Chemical reactions involving oxidation and influence the overall outcome. This article primarily features a IRR reduction processes at interfaces may vary from those in conventional liquid-phase or solid-phase reactions and could study on metal-ligand coordination at the solid-liquid interface. Of particular mention is the spontaneous reduction of Cu(II) to Cu(I) at a solid-liquid interface without the need of any extraneous reducing agent, unlike in the liquid-phase reaction whereby no reduction of Cu(II) to Cu(I) took place. As a consequence of the interfacial reduction reaction (IRR), thin films of Cu-TCNQ (tetracyanoquinodimethane) and Cu-HCF (hexacyanoferrate) were successfully deposited onto a thiol-functionalized Au substrate via a layer-by-layer (LbL) method. IRR is anticipated to be useful in generating new functional and stimuli-responsive materials, which are otherwise difficult to achieve via conventional liquid-phase reactions.