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We report on a novel type of Bi-doped crystal that exhibits ultrabroadband photoluminescence in the near infrared (NIR). Emission centers can be generated and degenerated reversibly by annealing the material in CO atmosphere and air, respectively, indicating that emission is related to the presence of Bi-species in low valence states. Correlating static and dynamic excitation and emission data with the size and charge of available lattice sites suggests that two types of Bi^0-species, each located on one of the two available Ba^2+ lattice sites, are responsible for NIR photoemission. This is further confirmed by the absence of NIR emission in polycrystalline Ca_2P_2O_7:Bi and Sr_2P_2O_7:Bi. Excitation is assigned to transitions between the doubly degenerated ground state ^4S_3/2 and the degenerated excited levels ^2D_3/2, ^2D_5/2 and ^2P_1/2, respectively. NIR emission is attributed to ^2D_3/2?^4S_3/2 …