We demonstrate that a copper(II) organic complex can control the electrical characteristics of conventional Au/n-Si metal–semiconductor (MS) contacts. We investigated the electronic and photovoltaic properties of a Cu(II) complex/n-Si heterojunction diode. The ideality factor n and barrier height Φ_b of the diode were 2.22 and 0.736eV, respectively. An ideality factor greater than unity indicates that the diode exhibits non-ideal current–voltage behavior. This behavior results from the effect of series resistance and the presence of an interfacial layer. The series resistance and barrier height determined using Norde’s method were 6.7 kΩ and 0.77eV, respectively. The device showed photovoltaic behavior, with a maximum open-circuit voltage of 0.24V and a short circuit current of 1.7 μA under light of 8mW/cm².