For the first time, lead film electrodes resistant to the action of oxidants commonly used to enhance the catalytic electrochemical response were deposited physically from a gaseous phase on thick film gold substrates and applied in catalytic adsorptive stripping voltammetry (CAdSV). The newly developed multilayer electrodes comprising a glass slide, an adhesive layer of titanium, a gold layer and finally, the working layer of lead were characterized by excellent CAdSV performance. Their sensitivity and reproducibility improved further after thermal pretreatment. The proposed sensor was sensitive (LOD = 0.002 μg L−1; tacc = 30 s) and the cobalt response was very reproducible (2.3%) and depended linearly on cobalt concentrations within the range of 0.06–1.05 μg L−1.