Diarylbutadiyne derivatives are ideal monomers for providing the -electron-conjugated system of polydiacetylenes (PDAs). The geometrical parameters for diacetylene topochemical polymerization are known. However, control of the molecules under these parameters is yet to be addressed. This work shows that by simply tailoring diarylbutadiyne with amide side-chain substituents, the arrangement of the substituents and the resulting hydrogen bond framework allows formation of -electron-conjugated PDA.