Multidrug and toxic compound extrusion (MATE) transporters are a family of cation antiporters occurring in most organisms from prokaryotes to eukaryotes. This family constitutes one of the largest transporter families in plants, with, for example, more than 50 MATE genes in the Arabidopsis genome. Moreover, MATE transporters are involved in a wide variety of physiological functions throughout plant development, transporting a broad range of substrates such as organic acids, plant hormones and secondary metabolites. This review categorizes plant MATE transporters according to their physiological roles and summarizes their tissue specificity, membrane localization, and transport substrates. We also review the molecular evolutionary development of plant MATE transporters.