Here we report on our investigations into the aggregation behaviour and optoelectronic properties of organic (semi)conductor-containing π-conjugated rod–coil–rod triblock materials. The facile synthesis of these rod-like tetra(aniline) (TANI) containing materials was achieved by a one-step condensation reaction of mono-functional phenyl/NH2 end-capped TANI and di-functional aliphatic diacyl chloride substrates. Simple variation of the n-alkyl spacer chain length impacted on the intermolecular amide-mediated H-bonding interactions and allowed fine-tuning of dc-conductivity values over two orders of magnitude for thin films of plasticized and CSA-doped supported thin films. Initial investigations into the production of anisotropic functional structures yielded micrometer-sized spherical (vesicular or solid spheres) isotropic functional structures. This approach is identified as an area for further exploration.