Oligoynes with two or more conjugated carbon-carbon triple bonds are useful precursors for carbon-rich nanomaterials. However, their range of app0lications has so far been severly limited by the challenging syntheses, particularly in the case of oligoynes with chemical functional groups. Here, we report a universal synthetic approach towards both symmetric and unsymmetric, functionalized hexaynes through the use of a modified Eglinton-Galbraith coupling and a sacrificial building block. We demonstrate the versatility of this approach by preparing hexaynes functionalized with phosphonic acid, carboxylic acid, ammonium, or thiol head groups, which serve as neutral, cationogenic, or anionogenic interfacially active groups. We show that these hexaynes are carbon-rich amphiphiles or bolaamphiphiles, that self-assemble at liquid-liquid interfaces, on solid surfaces, as well as in aqueous media.