The ion Ag2+ introduced into NaF shows a tetragonal electron paramagnetic resonance spectrum at 4.2 K which dynamically averages above 40 K. Uniaxial stress is used to show that the ground state is a strongly coupled E Jahn–Teller state. The well-resolved superhyperfine structure due to the F− neighbors is analyzed with a linear combination of atomic orbitals picture. Optical absorption of as-grown and treated crystals is further presented. The former ones show peaks at 202, 213, 219 nm due to Ag+. The latter ones present complex absorption spectra related to silver.