The study is based on the hypothesis that commercial catalogues of teaching materials are a fundamental source for historical research into the materials used in academic institutions, the production and distribution of equipment, and the teaching resources for educational practices. This paper covers a key period of Spanish educational history and seeks to set out, first, the concept and distinctive features of this source and offer a historiographic approach to the uses made of it. Secondly, it aims to analyse the characteristics of the sample studied and, thirdly, to examine the types of materials offered for the teaching of natural sciences, their emergence and evolution, as well as their introduction, dissemination and uses in Spanish secondary schools. © 2020 eum (Edizioni Università di Macerata, Italy).