The methods for synthesising polyacetylene are discussed and compared. As unsubstituted polymer is insoluble, precursor methods must be used to make films suitable for use in devices. While the fact that doped polyacetylene is conducting is of scientific interest, its instability and lack of luminescece has made it useless for practical applications. Substituted polyacetylenes can be made which are both soluble and luminescent, making them potentially useful in LEDs.The synthesis and properties of such polymers are discussed as well as their structure–property relationships and potential for use in devices.