The present invention provides novel methods and processes for polymerizing unsaturated substrates, such as alkyne bearing monomers, with arenes. The polymerizations are catalyzed by gold (Au) catalysts/complexes and/or other cocatalysts. The invention further provides novel structurally complex polymers prepared in high yield via an intermolecular polyhydroarylation mechanism. Such resulting products comprise oligomeric and polymeric materials with novel molecular architectures and microstructures, which subsequently impart unique properties. The invention includes both the synthesis methods and processes and the resulting compounds and compositions of matter.