The design and investigation of coordination polymers (CPs) attract tremendous interest around the world, which has recently been driven by the rapid growth of their practical use, especially in emerging fields such as green catalysis, energy conversion and storage, sensors, storage and transport of hydrogen. Among different strategies for preparation of CPs the use of alkoxides as chelating and bridging ligands has been successful in many cases. We also explored the potential of using both structure-directing aminoalcohols and carboxylates for the synthesis of CPs. The reaction of cobalt(II) isobutyrate with triethanolamine (H3tea) and azide ligands in MeCN media under heating lead to a mononuclear [Co(H3tea)2](is)2 (1) complex and a heterometallic [NaCo(H3tea)(is)3]n (2) coordination polymer (Figure 1). A single crystal X-ray diffraction analysis revealed that 1 crystalized in the Pbca space group with a = 9.203(5), b = 12.187(6), c = 23.525(4) Å, and consists of [Co(H3tea)2]2+ cations and hydrogen-bonded with the cations deprotonated isobutyric molecules. Each Co (II) atom in 1 is in a distorted octahedral N2O4 donor atom environment which comprises two N atoms and four O atoms from two H3tea ligands [CoN, 2.168 Å; CoO, 2.070 and 2.092 Å]. Crystals 2 are trigonal, space group P3221, a = b = 11.743(4), c = 31.912(11) Å, and reveal 1-D neutral waving chains which consist of the alternating Co(II) and Na(I) atoms linked by H3tea and isobutyrate bridging ligands (Fig. 1) and additionally stabilized by intramolecular Hbonds between oxygen atoms of H3tea and isobutyrate ligands. The six-coordinated geometries of Co(II) atoms in 2 are completed by three O atoms of three isobutyrates [CoOis, 2.050-2.078 Å], two O atoms [CoOalc, 2.146 and 2.174 Å] and an N atom [CoNalc, 2.200 Å] from H3tea ligand, forming distorted octahedra. Figure 1. Structure of [Co(H3tea)2](is)2 (1) (left) and [NaCo(H3tea)(is)3]n (2) (right).