In the search for new materials to fight against antibiotic-resistant bacteria, a hybrid composite from metallic copper nanoparticles (CuNPs) and a novel cationic pi-conjugated polyelectrolyte (CPE) were designed, synthesized, and characterized. The CuNPs were prepared by chemical reduction in the presence of CPE, which acts as a stabilizing agent. Spectroscopic analysis and electron microscopy showed the distinctive band of the metallic CuNP surface plasmon and their random distribution on the CPE laminar surface, respectively. Theoretical calculations on CuNP/CPE deposits suggest that the interaction between both materials occurs through polyelectrolyte side chains, with a small contribution of its backbone electron density. The CuNP/CPE composite showed antibacterial activity against Gram-positive (Staphylococcus aureus and Enterococcus faecalis) and Gram-negative (Escherichia coli and Salmonella enteritidis) bacteria, mainly attributed to the CuNPs' effect and, to a lesser extent, to the cationic CPE.