Two Ag(I)-based metal-organic compounds have been synthesized exploiting 4,6-bis(diphenylphosphino)pyrimidine (L). The reaction of this ligand with AgNO3 and AgBF4 in acetonitrile produces dinuclear complex, [Ag2L2(MeCN)2(NO3)2] (1) and 1D coordination polymer, [Ag2L(MeCN)3]n(BF4)2n (2), respectively. In complex 1, µ2-P,P′-bridging coordination pattern of the ligand L is observed, whereas its µ4-P,N,N′,P′-coordination mode appears in 2. Both compounds exhibit pronounced thermochromic luminescence expressed by reversible changing of the emission chromaticity from a yellow at 300 K to an orange at 77 K. At room temperature, the emission lifetimes of 1 and 2 are 15.5 and 9.4 µs, the quantum efficiency being 18 and 56%, respectively. On account of temperature-dependent experimental data, the phenomenon was tentatively ascribed to alteration of the emission nature from thermally activated delayed fluorescence at 300 K to phosphoresce at 77 K.