In this study, we report a straightforward and reproducible hydrothermal synthesis of copper oxide nanowires, their morphological and chemical characterization, and their application in gas sensing. Results show that the hydrothermal process is mainly influenced by the reaction time and the concentration of the reducing agent, demonstrating the synthesis of fine and long nanowires (diameter of 50–200 nm and length of 25 µm) after 10 h of reaction with 0.1 M of pyrrole. Two different annealing temperatures were tested (205 and 450 °C) and their effect on the morphology, chemical composition, and crystal size of the nanowires was analyzed by SEM, XPS, and XRD techniques, respectively. The analysis shows that the Cu2+ oxidation state is mainly obtained at the higher annealing temperature, and the nanowires’ shape suffers a transformation due to the formation of agglomerated crystallites. The gas sensing tests for acetone, ethanol, toluene, and carbon monoxide show preferential response and sensitivity to acetone and ethanol over the other analytes. The annealing temperature proves to have a higher influence on the stability of the nanowires than on their gas sensitivity and selectivity, showing better medium-term stability for the nanowires annealed at 450 °C.