Summary This paper deals with the first investigation concerning the thermal behaviour of Ni(II) complexes with ligands having biguanide moieties. The new complex [NiL(1)](ClO4)2·2.5H2O (1) with the Schiff base resulted in [2+1] condensation of N,N-dimethylbiguanide with pentane-2,4-dione (L(1)) and the complex [Ni2L(2)](ClO4)4 (2), with the Schiff base, L(2), resulted through the oxidative condensation of L(1) have been synthesized and characterised. The bonding and stereochemistry of the complexes have been characterized by IR and electronic spectra. The cyclic voltammograms show the characteristic waves for mononuclear and respectively binuclear Ni(II) complexes and indicate that both complexes exhibit catalytic effects on the CO2 electrochemical reduction. The thermal behaviour provided confirmation of the complexes composition as well as the number and the nature of water molecules and the intervals of thermal stability. The different nature of the ligands generates a different thermal behaviour for complexes.