The optical spectrum of gallium atoms produced and excited near a self‐formed high‐field emission tip of a liquid metal gallium ion source has been observed in detail. The spectrum reveals several interesting features. The dispersed neutral gallium lines exhibit asymmetric tails extending over tens of angstroms. The broadening is identified as due to quadratic stark effect. The maximum broadening is limited by field ionization of the atom from its excited state. The agreement with classical results is reasonable. A background continuum has also been observed, which may be due to transition radiation arising from collision of electrons, produced during field ionization, with the liquid‐metal tip.