The spectroscopic properties of several Ag+ activated strontium fluoride crystals—originating from different batches—were examined. Absorption, emission and excitation experiments including luminescence dynamics and polarization studies were performed at various temperatures. Four Ag+ related photoluminescent centers were found. Their properties are described. The predominant species in the asgrown crystals emits in the UV (at 315 nm) and was shown to be the single Ag+ ion in cubic surroundings. Two other centers emitting in the violet (400 nm) and in the yellow (550 nm), respectively, were attributed to (Ag+)2 pairs with different geometries. Models of these pseudo-molecular clusters are proposed. The nature of the system which produces a weak green (500 nm) luminescence remains open to questions.