The relaxation pathways of states in the energy region of the fundamental absorption of NaMgF3:Yb2+ and MgF2:Yb2+ are investigated using time-resolved vacuum ultraviolet spectroscopy. For NaMgF3:Yb2+, excitation into intrinsic free exciton states or above the band gap results in emission features associated with self-trapped excitons and impurity-trapped excitons. Excitation into host-related states of MgF2:Yb2+ similarly exhibits self-trapped exciton emission as well as emission from Yb2+ 4f135d states. The excitation features related to Yb2+ 4f14→4f135d transitions are interpreted using semi-empirical crystal field models. For both materials, the interplay between intrinsic distortions and Yb impurity centres, as the excitation wavelength and sample temperature are varied, is presented and analysed.