The Boltzmann constant is named after its 19th century Austrian discoverer, Ludwig Boltzmann. Although Boltzmann first linked entropy and probability in 1877, the relation was never expressed with a specific constant until Max Planck first introduced , and gave a more precise value for it (, about 2.5% lower than todays figure), in his derivation of the law of black-body radiation in 1900–1901. Before 1900, equations involving Boltzmann factors were not written using the energies per molecule and the Boltzmann constant, but rather using a form of the gas constant , and macroscopic energies for macroscopic quantities of the substance. The iconic terse form of the equation  on Boltzmanns tombstone is in fact due to Planck, not Boltzmann. Planck actually introduced it in the same work as his eponymous .
In 1920, Planck wrote in his Nobel Prize lecture:
This "peculiar state of affairs" is illustrated by reference to one of the great scientific debates of the time. There was considerable disagreement in the second half of the nineteenth century as to whether atoms and molecules were real or whether they were simply a heuristic tool for solving problems. There was no agreement whether chemical molecules, as measured by atomic weights, were the same as physical molecules, as measured by kinetic theory. Planck's 1920 lecture continued:
In versions of SI prior to the 2019 redefinition of the SI base units, the Boltzmann constant was a measured quantity rather than a fixed value. Its exact definition also varied over the years due to redefinitions of the kelvin (see ) and other SI base units (see ).
In 2017, the most accurate measures of the Boltzmann constant were obtained by acoustic gas thermometry, which determines the speed of sound of a monatomic gas in a triaxial ellipsoid chamber using microwave and acoustic resonances. This decade-long effort was undertaken with different techniques by several laboratories; it is one of the cornerstones of the 2019 redefinition of SI base units. Based on these measurements, the CODATA recommended  to be the final fixed value of the Boltzmann constant to be used for the International System of Units.