High sensitivity zinc oxide (ZnO) tetrapods (TPs) have been functionalized by nucleating cadmium sulphide (CdS) nanoparticles (NPs) directly on their surface with a spotted coverage thanks to an optimized synthesis in dimethylformamide (DMF). The obtained hybrid coupled material has been used to realize a gas sensing device with a highly porous nanostructured network, in which the proper alternation of ZnO-TPs and CdS-NPs gives rise to unconventional chemoresistive behaviours. Among the different tested gases and vapours, the sensor showed a unique fingerprint response-inversion between 300 °C and 400 °C only for nitrogen dioxide (NO2) and acetic acid (CH3COOH).