With orotic acid (H3OA) as building ligand, one one‐dimensional (1D) Zn(II) coordination polymer, [Zn2(HOA)(μ2‐OH)(μ3‐OH)(H2O)]n (1), and one tetra‐nuclear Cd(II) cluster, [Cd4(HOA)4(μ2‐OH2)2(H2O)10] (2), have been synthesized at 90 °C and room temperature, respectively. Single‐crystal X‐ray diffraction analyses reveal that complex 1 has an 1D stair‐stepping structure consisting of co‐edge bi‐rhomboid [Zn6] structural motif and μ3‐HOA2− linker, and 2 owns a quasi‐linear tetra‐nuclear [Cd4] cluster structure fastened by μ2‐OH2 and HOA2− fixators. The solid‐state photophysical properties were investigated and 1 and 2 display a distinct emission centered at 374 and 393 nm, respectively.