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Leaves of mate is one of the main non-timber forest products marketed in South America, which makes establishment of new plantations of great interest. However, vegetative propagation of mate plantlets presents difficulties, which may be associated with the complexity of adventitious root formation. The aims of this study were to anatomically characterize the adventitious roots of mate-clone mini-cuttings and investigate the relationship of phenols and starch with adventitious rooting competence in mini-cuttings treated or not with indole-butyric acid (IBA). The mini-cuttings of four clones were collected at 0, 30, and 60 days of cultivation, fixed in a solution containing 1% glutaraldehyde and 4% formaldehyde, pre-infiltrated and infiltrated in (2-hydroxyethyl) methacrylate, and sectioned in a microtome. Ferric chloride and toluidine blue were used to detect phenolic compounds and lugol to identify starch. Adventitious roots formed in mini-cuttings treated with IBA presented disorganized xylem and phloem and poles irregularly but exhibited sclerenchyma vessel elements and tracheid cells indicating functionality. Differences in the rhizogenic ability of mate clones mini-cuttings were not due to the presence of anatomical barriers or the accumulation of phenolic compounds but be associated with the presence and distribution of starch grains in vegetative propagules.