A new series of geometrically different complexes containing ferrocenyl hydrazone ligands were synthesised by reacting suitable precursor complex [MCl 2 (PPh 3 ) 2 ] with the ligands HL 1 or HL 2 (where M = Cu(II) or Ni(II); HL(5) and [Ni(L 2 ) 2 ] (6) were characterised by various spectral studies. Among them, complexes 3 and 5 characterised by single crystal X-ray diffraction showed a distorted tetrahedral structure for the former with 1 : 1 metal-ligand stoichiometry, but a distorted square planar geometry with 1 : 2 metal-ligand stoichiometry in the case of the latter. Systematic biological investigations like DNA binding, DNA cleavage, protein binding, free radical scavenging and cytotoxicity activities were carried out using all the synthesised compounds and the results obtained were explained on the basis of structure-activity relationships. The binding constant (K b ) values of the synthesised compounds are found to be in the order of magnitude 10 3 -10 5 M −1 and also they exhibit significant cleavage of supercoiled (SC) pUC19 DNA in the presence of H 2 O 2 as co-oxidant. The conformational changes of bovine serum albumin (BSA) upon binding with the above complexes were also studied. In addition, concentration dependent free radical scavenging potential of all the synthesised compounds (1-6) was also carried out under in vitro conditions. Assays on the cytotoxicity of the above complexes against HeLa and A431 tumor cells and NIH 3T3 normal cells were also carried out. † Electronic supplementary information (ESI) available: Crystal packing diagram of the unit cell of complexes 3 and 5 (Fig. S1 and S2), Electronic absorption spectra of binding of ligands 1 and 2 with DNA (Fig. S3), Electronic absorption spectra of binding of complexes 3, 4 and 5 with DNA (Fig. S4 and S5), Circular dichroism spectra of DNA and ligands 1 and 2 (Fig. S6), Circular dichroism spectra of DNA and complexes 3, 4 (Fig. S7), Emission spectra of binding of complexes 3, 4 and 5 with BSA (Fig. S8 and S9), Synchronous spectra (Δλ = 15 and 60 nm) of binding of complexes 3, 4 and 5 with BSA (Fig. S10, S11 and S12). CCDC reference numbers 796259 and 822888 for complexes 3 and 5.