The self-assembly of HL(L=[5-(ethoxycarbonyl)-4-phenyl-3,4-dihydropyrimidin-2(1H)-one-6-yl]methanesulfonate) with Sm(ClO4)3·6H2O yielded a 2D coordination polymer {[SmL3(H2O)2]·4H2O}n(1).Its crystallographic data indicated that it belonged to a triclinic system,space group P-1,a=1.42233(8),b=1.47155(8),c=1.53868(9) nm,α=8.62710(10),β=6.35250(10),γ=71.5790(10)°,V=2.7241(3) nm3,Z=2,R1=0.0693,wR2=0.1054.X-ray analysis revealed that the local coordination environment around Sm(III) was a slightly distorted dodecahedron in which Sm center was eight-coordinate geometry with eight oxygen atoms from three sulfonic groups,three carbonyl groups and two aqua ligands.Each L-acted as a bidentate spacer to link two Sm centers,resulted in the formation of a 2D hexagonally grid network.The discrete 2D planes in 1 were assembled into a 3D supramolecular network via strong hydrogen bonds among noncoordinated aqua O atoms,coordinated aqua O atoms,and noncoordinated O atoms of sulfonic groups and carbonyl groups.Furthermore,this metal-organic polymer exhibited strong photoluminescence maximized at 379 nm upon 274 nm excitation in the solid state at room temperature.