A series of bis(diphenylphosphino)alkanes complexes of tantalum (III) chloride of the type (TaCl6)-Cl-2[Ph-2-P(CH2)(n) - P-(Ch(2))(n) -P-Ph-2] (where n = 1 to 6) and Ta2Cl6[Ph-2-P-CH=CH-P-Ph-2] have been synthesised by the reaction of tantalum pentachloride with bis(diphenylphosphino) alkanes viz, 1,2-bis(diphenyl phosphino) methane(dppm), 1,2-bis(diphenyl phosphino)ethane (dppe), 1,3-bis(diphenyl phosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), 1,5-bis(diphenyl phosphino) pentane(dpppent), 1,6- bis(diphenyl phosphino)hexane (dpph), and cis-1,2-bis(diphenylphosphino)ethylene (dppen). The complexes have been characterised by elemental analysis, magnetic moment data, IR, H-1, P-31 and (NMR)-N-13 spectral studies.