A series of complexes [Cu(L)(CH3COO)2]·nH2O (L: isonicotinic acid 2-(2-hydroxy-8-substituted-tricyclo[7.3.1.02.7]tridec-13-ylidene)-hydrazones) were synthesised and characterised. The features of complexes have been assigned from microanalytical data, ESI–MS, IR, UV–Vis–NIR and EPR spectra, as well as thermal analysis. The ligands (hydrazones and acetate) act as chelate in the octahedral distorted complexes of Cu(II). The thermal analysis evidenced complex thermal transformations such as thermolises and oxidative degradation of hydrazone moiety as well as acetate into carbonate transformation, followed by carbonate decomposition up to CuO. The complexes were evaluated for their interaction with microbial and immortalised human cells, in order to formulate some potential biomedical applications, beyond the antimycobacterial activity.