Potential impact of copper replacing silver in the paste used for the front electrode fabrication in crystalline silicon solar cells was investigated. The copper was applied as a new CuXX component with about 2 wt.% to 6 wt.% share of XX modifier. The generated CuXX molecules were analyzed using transmission microscopy. Based on the commercial Du Pont PV19B paste, CuXX and XX materials, the new PV19B/CuXX paste with 51 wt.% share of Cu and the PV19B/XX paste with 51 wt.% share of XX only were developed. Comparative studies of the effect of the commercial PV19B paste made by DuPont Company, and the pastes with the CuXX component and with the modifier XX alone on the electrical parameters of solar cells produced on crystalline silicon were carried out. The solar cells were characterized by the current-voltage technique. As a final result, the Cz-Si solar cell with the 51 wt.% share of Cu in the front electrode having a series resistance of 0.551 Ω·cm2, an efficiency of 14.08 % and, what is more important, the fill factor of 0.716, was obtained. It is the best result ever obtained concerning direct Cu application for solar cells fabricated in thick-film technology.