Fac‐bis(ethanolamine)orotatonickel(II), [Ni(HOr)(ea)2] and mer‐bis(ethanolamine)orotatocopper(II) dihydrate, [Cu(HOr)(ea)2]· 2H2O were synthesized and characterized by elemental analysis, FT‐IR, UV‐Vis Spectroscopy and thermal analysis. In addition, their solid‐state structures were determined by single crystal X‐ray diffraction studies. Both the fac‐[Ni(HOr)(ea)2] (1) and mer‐[Cu(HOr)(ea)2]·2H2O (2) complexes are isomorphous and crystallize in the triclinic space group $P {\bar 1}$. The Ni2+ and Cu2+ ions are coordinated by two neutral ea ligands and one orotate dianion in a distorted octahedral fashion. The ea ligand acts as a bidentate donor through the amine N and hydroxyl O atoms, while orotate dianion is coordinated through deprotonated N3 pyrimidine atom and carboxylate oxygen atom as a bidentate ligand. Thermal decompositions of the complexes are studied in over the range 20–600 °C on heating in a static air atmosphere.