First examples of amphiphilic alkyl pentakis(phenylethynyl)benzene ethers containing functional groups at the terminal position of their alkoxy chains were synthesized by etherification of pentabromophenol with 11-bromoundecan-1-ol and 11-bromoundecanoic acid ethyl ester, respectively, and subsequent palladium catalyzed, fivefold coupling reactions with the substituted phenylacetylene. Two undecanoic acid derivatives with different pentakis(phenylethynyl)phenoxy substituents in the ω-position were prepared by ester cleavage from the corresponding ethyl esters. The thermal behaviours of five penta-alkynes in their pure states, as well as of their charge transfer complexes formed from mixtures with 2,4,7-tri-nitrofluorenone, were examined.