Matrix isolation has its origins in the first half of the 20th century with the experiments by photo-chemists and physicists freezing samples in liquefied gases. The earliest isolation experiments involved the freezing of species in transparent, low temperature organic glasses, such as EPA (ether/isopentane/ethanol 5:5:2). The modern matrix isolation technique was developed extensively during the 1950s, in particular by George C. Pimentel. He initially used higher-boiling inert gases like xenon and nitrogen as the host material, and is often said to be the "father of matrix isolation".
Laser vaporization in matrix isolation spectroscopy was first brought about in 1969 by Schaeffer and Pearson using a yttrium aluminum garnet (YAG) laser to vaporize carbon which reacted with hydrogen to produce acetylene. They also showed that laser-vaporized boron would react with HCl to create BCl. In the 1970s, Koerner von Gustorfs lab used the technique to produce free metal atoms which were then deposited with organic substrates for use in organometallic chemistry. Spectroscopic studies were done on reactive intermediates in around the early 1980s by Bell Labs. They used laser-induced fluorescence to characterize multiple molecules like SnBi and SiC. Smalleys group employed the use of this method with time-of-flight mass spectrometry by analyzing Al clusters. With the work of chemists like these, laser-vaporization in matrix isolation spectroscopy rose in popularity due to its ability to generate transients involving metals, alloys and semi-conductor molecules and clusters.