Poly-yne polymers containing transition metals are an interesting class of materials for their chemical and physical properties. In order to better understand the properties of such materials, a good knowledge of their structure is necessary. In this study we have determined the local structure around Pd in Pd-diethynylbiphenyl (Pd-DEBP, [Pd(PBU3)(2)C16H4](n)) polymer containing a diethynylbiphenyl unit as the organic spacer. Thin films of the material were deposited onto a Cr substrate and were studied by means of extended X-ray absorption structure spectroscopy (EXAFS) in total reflection mode. The bond lengths between Pd and its neighbors as well as the C-C distances in the linear chain are determined and compared with literature data reported for model complexes. (C) 2004 Elsevier B.V. All rights reserved.