Using two ligands, 4,6-bis(2-pyridyl)-2-aminopyrimidine (L1) with two N,N'-chelating sites and 4-(2-pyridyl)-6-(4pyridyl)-2-aminopyrimidine (L2) (as the isomer of L1) containing one chelating site and one bridging unit, a series of novel Ag(I) complexes varying from zero- to two-dimensions have been prepared and their crystal structures determined via single-crystal X-ray diffraction. The two ligands are employed for the first time in coordination chemistry. The structures of compounds 1-3 are directed by the counteranions adopted in the reaction system: The reaction of L1 with AgNO3 yielded a dimer [Ag(2)L1(2)](NO3)(2) (1). The reaction of L1 with AgCF3SO3 led to a one-dimension "V-shaped" chain {[AgL1](CF3SO3)}(n) (2). When AgSCN was used, a one-dimension ladder {[Ag(2)L1-(SCN) 2](H2O)-H-.} n (3) was obtained. While ligand L2 reacted with AgNO3, a two-dimension {[Ag-2(L-2)(2)](NO3)(2), H2O}(n) (4) was prepared with the help of an argentophilic interaction. Compounds 1-4 display room-temperature photoluminescence.