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Donato García was the mineralogy professor at the Royal Cabinet of Natural History and Central University of Madrid from 1816 to 1853. In addition to teaching mineralogy, he gathered geological and mineralogical material for didactic purposes, and for exhibitions in the hall of the Cabinet. He was a key figure in developing the subject matter of mineralogy in Spain during the first half of the nineteenth century. Donato Garcia likewise promoted the careers of very important future teachers at the Military Academy of Engineers, Natural Sciences Museums, and Universities, integrating oral lectures, mineral testing, visual recognition, and the use of crystallographic models. This paper investigates how the crystallographic system proposed by Haüy (in the mid-thirties) was assimilated through unpublished documents of Donato García’s mineralogical lessons from 1824 to 1825, obtained from Spain’s Archivo General de Palacio (Madrid). Hence, this manuscript can be considered the first scientific work reliably attributable to Donato and based on the notes of his pupil José Musso y Valiente, which stands as an early attempt to create a handbook of mineralogy in Spanish. The novel approach to teaching mineralogy is furthermore compared with lessons published by disciple Antonio María Cisneros y Lanuza in 1843. Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature.