Monodispersed CuO octahedral crystals were successfully synthesized using a low-temperature co-precipitation method. Zinc doping in CuO created surface defects that enhanced oxygen adsorption on the surface crucial for gas sensing applications. Pure and Zn-doped CuO sensor films were realized using the doctor blade method. The sensor films showed selective response towards a low concentration of NO₂ at a lower operating temperature of 150 °C. Doping with Zn causes the resistance of the sensor film to decrease due to the enhancement of charge carriers with an analogous improvement in the sensor response. The observed decrease in sensor resistance agreed well with the findings of the work function studies. Zinc doping resulted in an increase in work function by 180 meV which, after NO₂ exposure, was found to increase by a further 130 meV, attributed to the oxidizing behavior of the test gas.