A new oligophenyleneethynylene (OPE)based Pd(II) pyridyl complex has been synthesized, and its self-assembly has been investigated in solution, in the bulk state, and on surfaces. Detailed analysis of concentration- and temperature-dependent UV-vis studies in methylcyclohexane supported by DFT calculations demonstrate for the first time that cooperative supramolecular polymerization processes can be driven by metallophilic interactions.