Four new Ni(II) complexes [Ni2(Msal-tsc)2(μ-dppm)] (1), [Ni2(Msal-mtsc)2(μ-dppm)] (2), [Ni2(Msal-etsc)2(μ-dppm)] (3) and [Ni2(Msal-ptsc)2(μ-dppm)] (4) containing 3-methoxy-salicylaldehyde-4(N)-substituted thiosemicarbazones having the general formula [H2-MSal-tsc-R],(where R=H, Me, Et or Ph) and 1,1′-bis(diphenylphosphino)methane (dppm) were synthesized and characterized by various spectral, analytical techniques and X-ray crystallography. Crystallographic studies of the complexes 1 and 3 revealed the square planar geometry around the nickel ion. The binding ability of the complexes with CT-DNA was carried out by absorption/emission titration and which an intercalative mode of binding was observed. Further, their ability to interact with BSA protein has been explored. Investigations of antioxidation properties showed that all the compounds have strong radical scavenging properties. Further, anticancer activity of the compounds on the lung cancer cell line A549 has also been investigated. From the results it is observed that the complexes (2 (IC50=23μM), 3 (IC50=12μM) & 4 (IC50=20μM)) exhibited a significant anticancer activity over complex 1 (IC50=26μM), ligands, NiCl2·6H2O and the standard drug, Cisplatin (IC50=25μM).