Dating back to the nineteenth century there are reports of these particles by authors such as Jacques-Louis Bournon in 1813 for marcasite, and Gustav Rose in 1831 for gold.  In mineralogy and the crystal twinning literature they are referred to as a type of cyclic twins where a number of identical single crystal units are arranged in a ring-like pattern where they all join at a common point or line. The name  comes from them having five members (single crystals).  The older literature was mainly observational, with information on many materials documented by Victor Mordechai Goldschmidt in his Atlas der Kristallformen. Drawings are available showing their presence in marcasite, gold, silver, copper and diamond. New mineral forms with a fiveling structure continue to be found, for instance pentagonite, whose structure was first decoded in 1973, is named because it is often found with the five-fold twinning.
Most modern analysis started with the observation of these particles by Shozo Ino and Shiro Ogawa in 1966-67, and independently but slightly later (which they acknowledged) work by John Allpress and John Veysey Sanders. In both cases these were for vacuum deposition of metal onto substrates in very clean (ultra-high vacuum) conditions, where nanoparticle islands of size 10-50 nm were formed during thin film growth. Using transmission electron microscopy and diffraction these authors demonstrated the presence of the five single crystal units in the particles, and also the twin relationships. They also observed single crystals and a related type of icosahedral nanoparticle. They called the five-fold and icosahedral crystals multiply twinned particles (MTPs). In the early work near perfect decahedron (pentagonal bipyramid) and icosahedron shapes were formed, so they were called decahedral MTPs or icosahedral MTPs, the names connecting to the decahedral () and icosahedral () point group symmetries. Parallel, and apparently independent there was work on larger metal whiskers (nanowires) which sometimes showed a very similar five-fold structure, an occurrence reported in 1877 by Gerhard vom Rath. There was fairly extensive analysis following this, particularly for the nanoparticles, both of their internal structure by some of the first electron microscopes that could image at the atomic scale, and by various continuum or atomic models as cited later.
Following this early work there was a large effort, mainly in Japan, to understand what were then called "fine particles", but would now be called nanoparticles. By heating up different elements so atoms evaporated and were then condensed in an inert argon atmosphere, fine particles of almost all the elemental solids were made and then analyzed using electron microscopes. The decahedral particles were found for all face centered cubic materials and a few others, often together with other shapes.While there was some continuing work over the following decades, it was with the National Nanotechnology Initiative that substantial interest was reignited. At the same time terms such as pentagonal nanoparticle, pentatwin, or five-fold twin became common in the literature, together with the earlier names. A large number of different methods have now been published for fabricating fivelings, sometimes with a high yield but often as part of a larger population of different shapes. These range from colloidal solution methods to different deposition approaches. It is documented that fivelings occur frequently for diamond, gold and silver, sometimes for copper or palladium and less often for some of the other fcc metals such as nickel. There are also cases such as pentagonite where the crystal structure allows for five-fold twinning with minimal to no elastic strain (see later). There is work where they have been observed in colloidal crystals consisting of ordered arrays of nanoparticles, and single crystals composed on individual decahedral nanoparticles. There has been extensive modeling by many different approaches such as embedded atom, many body, molecular dynamics, tight binding approaches, and density functional theory methods as recently discussed by Francseca Baletto and Riccardo Ferrando and also discussed for energy landscapes later.