End-group-modified poly(3-hexylthiophenes) (P3HT) with complex hydrogen-bonding moieties have been prepared starting from telechelic alkyne-functionalized P3HT via a copper(I) catalyzed azide/alkyne "click" reaction. The final polymers are projected to arrange into pseudoblock copolymers consisting of alternating donor/acceptor polymers for application in solar cell materials. Starting from a bromine-telechelic P3HT (M-n = 2000 g/mol; M-w/M-n = 1.2) prepared via the McCullough method followed by additional bromination reaction yielding telechelic P3HTs with (80% Br/Br; 20% H/Br) end groups, the respective alpha,omega)-(trimethylsilyl)ethynyl-P3HTs were prepared via Sonogashira coupling reactions. Analysis of the end groups of the alkynyl-telechelic P3HT species was achieved by use of LC-ESI-TOF methods for the first time, proving the formation of similar to 59% (ethynyl/ethynyl) and similar to 40% (ethynyl/H) species within the alpha,omega-(trimethylsilyl)ethynyl-P3HTs, with only minor amounts (similar to 1%) of the respective (H/H)-modified species. Additionally, MALDI methods were used for a qualitative assessment. Subsequent azide/alkyne "click" reaction with either 1-(6-azidohexyl)thymine or 5-((4-azidobenzoyl)amino)-N,N'(6-(octanoylamino)pyridin-2-yl)isophthalam ide using Cul, CuBr(PPh3)(3), or Cul center dot P(OEt)(3) as catalyst yielded the final products with attached hydrogen bonds as judged by LC-ESI-TOF methods. The described method opens an access toward supramolecular P3HT polymers with hydrogen-bonding moieties.