A silver(I) complex [Ag(chlsp)2](CF3CO2),(chlsp=(E)-4-(4-chlorostyryl) pyridine),was synthesized by the reaction between AgCF3CO2 and chlsp in the anhydrous enthnol. The crystal structure of [Ag(chlsp)2](CF3CO2) was characterized by elemental analysis,IR and determined by using single crystal X-ray diffraction. The result shows that the complex crystallize in triclinic system,with space group P1,a=0.109 7(2) nm,b=0.111 7(2) nm,c=0.117 2(2) nm,α=73.60(3)°,β=85.03(3)°,γ=81.82(3)°,V=0.136 2(4) nm3,Z=2. The moleculars are connected by Ag…Ag and Ag…Cl interactions,resulting in a three-dimensional network.