The problem of copper diffusion in semiconductor devices has been known for several decades as copper has been used as an interconnecting (bonding) metal and has been intensively studied due to its high diffusion coefficient. The influence of the intensive diffusion of copper, depending on the technology of the deposition regimes, has been investigated in thin-film solar cells based on copper, zinc, and titanium oxides obtained by DC-reactive magnetron sputtering. The observed effect significantly changes the structure of the CuO films and affects the properties of the TiO₂:ZnO/CuO photocell. The composition of the layers and the copper diffusion in the photocells were studied using a cross-section obtained by scanning electron microscopy (SEM). The influence of the copper diffusion in the layers on the current–voltage (I-V) and power–voltage (P-V) characteristics and optical properties was investigated. The photoelectric behavior of two structures of thin-film solar cells was confirmed through -V research. The values of the open-circuit voltage (V_OC) and short-circuit current density (J_SC) of photovoltaic devices reached (11 ÷ 15) mV and (6.1 ÷ 6.8) μA, respectively. Furthermore, the Pmax, FF, RS, and RSH values were calculated and analyzed. The difference in the composition of the upper layer of the structure caused changes in the reflection spectra in the wavelength range of 190–2500 nm and, depending on the wavelength, varies in the range of 0–27%.