A systematic study has been carried out for the use of the palladium-based Extended One Pot (EOP) synthetic protocol toward the preparation of metal alkynyl oligomers of general formula [ C C Ar C C M(L) m ] n (M=Pt, Pd). Model compounds of type trans-M(PBu 3 ) 2 (C CC 6 H 5 ) 2 have been prepared by the reaction of tributyltinethynylbenzene with trans-M(PBu 3 ) 2 Cl 2 , in the absence of palladium catalysis, since the presence of catalytic Pd(PPh 3 ) 4 yields reaction mixtures containing starting material, product and intermediate complex trans-MCl(PBu 3 ) 2 (C CC 6 H 5 ). Palladium catalysis has been used for the formation of the bistinacetylide compounds Bu 3 Sn C C Ar C C SnBu 3 (Ar=C 6 H 4 ; bis(2,5-n-octyloxy)C 6 H 4 ). Subsequent coupling of these compounds with MCl 2 (PBu 3 ) 2 in the absence of palladium catalyst yields metal alkynyl oligomers. Comparison of 3 1 P-NMR and gel permeation chromatography (GPC) analyses indicates that the GPC technique represents a reliable method to estimate polymer chain lengths for polymers bearing branched aromatic spacers, in spite of the rigid-rod shape of the polymer backbone. Single crystal X-ray determinations of model compounds demonstrate the essential role of side substituents in the aromatic ring to control the supramolecular order and, as a consequence, the optoelectronic properties of materials.