Quantum tunneling was developed from the study of radioactivity which was discovered in 1896 by Henri Becquerel. Radioactivity was examined further by Marie Curie and Pierre Curie, for which they earned the Nobel Prize in Physics in 1903. Ernest Rutherford and Egon Schweidler studied its nature, which was later verified empirically by Friedrich Kohlrausch. The idea of half-life and the possibility of predicting decay was created from their work.

In 1901, Robert Francis Earhart discovered an unexpected conduction regime while investigating the conduction of gases between closely spaced electrodes using the Michelson interferometer. J. J. Thomson commented that the finding warranted further investigation. In 1911 and then 1914, then-graduate student Franz Rother directly measured steady field emission currents. He employed Earhart's method for controlling and measuring the electrode separation, but with a sensitive platform galvanometer. In 1926, Rother measured the field emission currents in a "hard" vacuum between closely spaced electrodes

Quantum tunneling was first noticed in 1927 by Friedrich Hund while he was calculating the ground state of the double-well potential. Leonid Mandelstam and Mikhail Leontovich discovered it independently in the same year. They were analyzing the implications of the then new Schrödinger wave equation.

Its first application was a mathematical explanation for alpha decay, which was developed in 1928 by George Gamow (who was aware of Mandelstam and Leontovich's findings and independently by Ronald Gurney and Edward Condon. The latter researchers simultaneously solved the Schrödinger equation for a model nuclear potential and derived a relationship between the half-life of the particle and the energy of emission that depended directly on the mathematical probability of tunneling.

After attending a Gamow seminar, Max Born recognised the generality of tunneling. He realised that it was not restricted to nuclear physics, but was a general result of quantum mechanics that applied to many different systems. Shortly thereafter, both groups considered the case of particles tunneling into the nucleus. The study of semiconductors and the development of transistors and diodes led to the acceptance of electron tunneling in solids by 1957. Leo Esaki, Ivar Giaever and Brian Josephson predicted the tunneling of superconducting Cooper pairs, for which they received the Nobel Prize in Physics in 1973. In 2016, the quantum tunneling of water was discovered.