Electrochemical sensors have shown potential in recent years for plant species identification and phylogenetic studies. These works have been used to investigate the affinities of different species in many genera. However, the ability of electrochemical sensors to study relationships between different genera within a family has not been investigated. In this work, we selected 31 species in the Labiatae and 5 exotaxa as subjects to investigate the feasibility of electrochemical sensors at the genus level. The results show that electrochemical sensors are still very effective for the identification of these plants. Different pattern recognition techniques can make the identification more efficient. Also, the fingerprint profiles collected by the sensors can be used for phylogenetic studies of Labiatae. The phylogram divides all the species into five clusters, where the exotaxa are in one cluster. Species in the Labiatae are mainly distributed in four other clusters. Importantly, the different genera of species all showed close affinities, representing that electrochemical fingerprinting can well distinguish the affinities between the different genera. The results of this work demonstrate the great potential of electrochemical sensors in the study of plant phylogeny. Its application is not limited to the study at the species level, but can be extended to the genus level.