We report the synthesis and characterisation of eight molecules that have in common a diphenylphosphino group bonded to an α-carbon atom of a thienyl or pyridyl ring: 5,5′-bis(diphenylphosphino)-2,2′-bithiophene 1; diphenyl(2,2′-bithienyl-5-yl)phosphine 2; 5,5″-bis(diphenylphosphino)-2,2′:5′,2″-terthiophene 3; diphenyl(2,2′:5′,2″-terthienyl-5-yl)phosphine 4; diphenyl[5-(2′-pyridyl)-2-thienyl]phosphine 5; diphenyl[6-(2′-thienyl)-2-pyridyl]phosphine 6; diphenyl{5-[6′-(diphenylphosphino)-2′-pyridyl]-2-thienyl}phosphine 7; and 2,6-bis[5′-(diphenylphosphino)-2′-thienyl]pyridine 8. Methods used for their synthesis range from lithiation of the parent heterocycle and subsequent reaction with PPh₂Cl to the use of coupling reactions catalysed by metal complexes to assemble the molecule from its subunits. The crystal and molecular structures of 1, 7 and 8 have been determined and show that the 2,2′-bithienyl moiety in 1 adopts an s-trans-conformation, while the 2-(2′-thienyl)pyridyl moieties in 7 and 8 adopt s-cis-conformations in the solid state. These compounds represent a new series of ligands that are expected to bond to metals through the phosphorus and/or nitrogen atoms rather than a sulfur atom, in view of the poor donor ability of a thiophene sulfur towards metals.