[2][3] Early work in the field of polyacetylene research was aimed at using doped polymers as easily processable and lightweight "plastic metals".

Compounds called polyacetylenes also occur in nature, although in this context the term refers to polyynes, compounds containing multiple acetylene groups ("poly" meaning many), rather than to chains of olefin groups ("poly" meaning polymerization of).

The controlled synthesis of each isomer of the polymer, cis-polyacetylene or trans-polyacetylene, can be achieved by changing the temperature at which the reaction is conducted.

Despite the conjugated nature of the polyacetylene backbone, not all of the carbon–carbon bonds in the material are equal: a distinct single/double alternation exists.

[8] After this first reported synthesis, few chemists were interested in polyacetylene because the product of Natta's preparation was an insoluble, air sensitive, and infusible black powder.

They discovered that the polymerization of polyacetylene could be achieved at the surface of a concentrated solution of the catalyst system of Et3Al and Ti(OBu)4 in an inert solvent such as toluene.

This method allows control over the structure and properties of the final polymer by varying temperature and catalyst loading.

[13] Mechanistic studies suggest that this polymerization involves metal insertion into the triple bond of acetylene.

[14] By varying the apparatus and catalyst loading, Shirakawa and coworkers were able to synthesize polyacetylene as thin films, rather than insoluble black powders.

[15] Enkelmann and coworkers further improved polyacetylene synthesis by changing the catalyst to a Co(NO3)2/NaBH4 system, which was stable to both oxygen and water.

[8] Polyacetylene can be synthesized by ring-opening metathesis polymerisation (ROMP) from cyclooctatetraene, a precursor that is more expensive but easier to handle than the acetylene monomer.

[16] This synthetic route also provides a means for introducing solubilizing groups to the polymer while maintaining the conjugation.

[4] Polymers with linear groups such as n-octyl had high conductivity but low solubility, while highly branched tert-butyl groups increased solubility but decreased conjugation due to polymer twisting to avoid steric crowding.

Short, irregular segments of polyacetylene can be obtained by dehydrohalogenation of poly(vinyl chloride):[17] More efficient methos for synthesizing long polyacetylene chains exist and include the Durham precursor route in which precusor polymers are prepared by ring-opening metathesis polymerization, and a subsequent heat-induced reverse Diels–Alder reaction yields the final polymer, as well as volatile side products.

[18] Polyacetylene doped with (p-type) dopants retain their high conductivity even after exposure to air for several days.

[8] As with p-type dopants, charge-transfer complexes are created, where the polymer backbone is anionic and the donor is cationic.

[8] Lower catalyst loadings leads to the formation of dark red gels, which can be converted to films by cutting and pressing between glass plates.

While both cis and trans-polyacetylene show high thermal stability,[20] exposure to air causes a large decrease in the flexibility and conductivity.