Correlation between the photophysics and the structures of three Ag(I)-bis(diphosphine) complexes ([Ag(dppbz)(2)]NO3 (1 center dot NO3), [Ag(dppe)(2)]NO3 (2 center dot NO3), and [Ag(dppp)(2)]NO3 (3 center dot NO3) (dppbz = 1,2-bis(diphenylphosphino)benzene, dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane) has been investigated using temperature-dependent emission measurements and electrochemical and theoretical methods. All three Ag(l)-bis(diphosphine) complexes have relatively low oxidation potential, which allows metal-to-ligand charge transfer (MLCT) contribution in the lowest excited state of the tetrahedral geometry, which is difficult in other Ag(I) complexes. Both 1 center dot NO3 and 2 center dot NO3 show orange phosphorescence with moderate quantum yield in air-free methanol at room temperature, while 3 center dot NO3 is less emissive in solution at room temperature. In all three complexes the temperature-dependent luminescence measurements in EtOH/MeOH 4:1 (v/v) solution indicate the blue-shift of the emission maximum and the increase of the emission intensity on lowering the temperature. In particular, the sequential emission spectral change with decreasing temperature isobserved in 1 center dot NO3 and 2 center dot NO3. In the glass state at 90 K, all three complexes show intense blue phosphorescence. The theoretical calculation using density functional theory (DFT) suggests that the orange and blue emissions mainly originate from the 3 MC excited state based on a square-planar geometry and the (IL)-I-3+(MLCT)-M-3 excited state based on a tetrahedral geometry, respectively.