Two　novel　silver(I)　complexes　[Ag2Br2(DPEphos)(2)(dppe)](1)　and　[Ag(DPEphos)(dppe)]NO3(2)　(DPEphos=his　[2-(diphenylphosphino)phenyl]ether,　dppe　=bis　(diphenylphosphino)ethane)　have　been　synthesized　and　characterized　by　IR,　single-crystal　X-ray　diffraction,　H-1　NMR,　P-3　NMR　spectroscopy　and　fluorescence　spectra.　1　is　comprised　of　AgBr,　DPEphos　and　dppe　in　2:2:1　molar　ratio　generating　a　binuclear　complex.　The　dppe　ligand　bridges　two　Ag　atoms　through　two　P　atoms　in　1.　While,　2　is　obtained　by　the　reactions　of　AgNO3,DPEphos　and　dppe　in　1:1:1　molar　ratio　generating　a　sample　mono-nuclear　complex.　The　Ag(I)　atom　is　chelated　by　DPEphos　and　dppe　ligand.　In　the　P-31　NMR　spectra　of　2,　there　are　four　splitting　signals　(doublets　or　triplets).　The　luminescent　spectra　show　that　the　origin　of　these　emissions　all　involves　emissive　state　derived　from　ligand　centered　pi-pi*　transition.　CCDC:　1043375,　1;　1043376,　2.