We report on the detection of a metastable He i* absorption line at 3889 Å in a spectrum of ζ Ophiuchi from the Ultraviolet and Visual Echelle Spectrograph with an extremely high signal-to-noise ratio (∼3500), which was collected using the 8-m telescope UT2 at Paranal. We cannot conclusively determine whether the He i* absorption arises within the H ii region or within the foreground H i clouds, which are responsible for interstellar CH, CH+, Na i, Ca ii, K i, etc., absorption, because the radial velocities of the main mass of gas are nearly identical in both regions. The measured equivalent width (1.0 ± 0.07 mÅ) of the line gives a column density of 1.158(± 0.081) × 1011 cm−2, when we assume the absence of saturation effects, and an oscillator strength of f= 0.0645. We estimate the ionization rate of helium to be 1.491 × 10−13, if the helium relative abundance in the H i cloud (with respect to hydrogen) is solar, and 7.475 × 10−14 cm−2, if the helium abundance is enhanced by the nearby star.