2-(3-Ferrocenylthienyl)phosphines of type 2-PR2-3-Fc-(C4H2S)-C-c (R = Bu-t (2); R = Ph (3); Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) were synthesized and the structures of 2 and 3 in the solid state were determined by single X-ray structure analysis. Inter- and intra-molecular T-shaped pi center dot center dot center dot pi stackings involving cyclopentadienyl and phenyl rings are characteristic for 3. The application of 2 and 3 as ligands in the Pd-catalyzed Suzuki-Miyaura C,C cross-coupling of aryl halides with boronic acids to give the respective biaryls is reported. Electron-rich, electron-poor and sterically hindered substrates could be coupled with high yields at Pd-loadings as low as 0.1 mol%. (C) 2015 Elsevier B.V. All rights reserved.