The first record of the pyroelectric effect was made in 1707 by Johann Georg Schmidt, who noted that the "[hot] tourmaline could attract the ashes from the warm or burning coals, as the magnet does iron, but also repelling them again [after the contact]". In 1717 Louis Lemery noticed, as Schmidt had, that small scraps of non-conducting material were first attracted to tourmaline, but then repelled by it once they contacted the stone. In 1747 Linnaeus first related the phenomenon to electricity (he called tourmaline Lapidem Electricum, "the electric stone"), although this was not proven until 1756 by Franz Ulrich Theodor Aepinus.
Research into pyroelectricity became more sophisticated in the 19th century. In 1824 Sir David Brewster gave the effect the name it has today. Both William Thomson in 1878 and Woldemar Voigt in 1897 helped develop a theory for the processes behind pyroelectricity. Pierre Curie and his brother, Jacques Curie, studied pyroelectricity in the 1880s, leading to their discovery of some of the mechanisms behind piezoelectricity.
It is mistakenly attributed to Theophrastus (c. 314 BC) the first record of pyroelectricity. The misconception arose soon after the discovery of the pyroelectric properties of tourmaline, which made mineralogists of the time associate the legendary stone Lyngurium with it. Lyngurium is described in the work of Theophrastus as being similar to amber, without specifying any pyroelectric properties.