Ethnopharmacological relevance Most ethnobotanical research bases its analyses on individual taxa catalogues and their uses, rather than on mixtures. However, mixtures constitute an important chapter of our different lines of research and they represent a large volume of information. The relevance of these data in folk medicine could be explained as a response to the cure of multicausal etiology diseases or by a possible polyvalent effect of the mixture as opposed to the effect of each taxon alone. Aims of the study The main goals are: i) to perform qualitative and quantitative analyses of these mixtures; ii) to carry out a comparison among the mixtures in two Catalan territories and their floristic composition; iii) to assess the worth of families association; and, iv) to evaluate whether the plants claimed to be used in mixtures have contraindications or possible negative interactions according to phytopharmaceutical literature. The ultimate goal is to test a protocol that can be implemented in similar studies. Materials and methods We have used data on medicinal plant mixtures obtained from two extensive ethnobotanical field studies carried out in two Catalan districts, Alt Empordà and Ripollès. The quantitative analyses by means of descriptive statistics were carried out with Excel. New contributions like the implementation of the Shannon index to quantify the diversity of families in plant combinations, the creation of a new index to calculate the taxon importance in mixtures, or the use of a social network analysis to study the connection between botanical families have been employed in this work. Results In total, a set of 484 mixtures from Alt Empordà and Ripollès (Catalonia, Iberian Peninsula) have been analysed: 462 for human use and 22 for veterinary. Thymus vulgaris and Rosmarinus officinalis are among the most commonly used species in mixtures. The aerial part of the plant is the most used, and the anticatarrhal usage is the most frequent in both territories. A wide diversity of families has been observed in mixtures and reflects a strong bond between the number of taxa and the number of families in each mixture, being almost equal to one. The Shannon diversity index applied to mixtures has the maximum value at 0.86. No exclusive plants are used in mixtures, as reflected on the index of taxon usefulness in mixtures (ITUM), proposed in the present work. The association of families is strong between Lamiaceae (12.12%) and Asteraceae with Lamiaceae (11.69%). Finally, the informant consensus factor (0.85) reflects the strong consistency of data reported by the interviewees. Conclusions The present analysis has confirmed that it is possible to study the data of plants in mixtures as thoroughly as when they are considered in isolation in an ethnofloristic catalogue, and maybe this kind of ethnobotanical investigation could be a first step for future pharmacological studies that may result in a relevant complement to the current phytotherapy market.