The use of crystal engineering to control the supramolecular arrangement of pi-conjugated molecules in the solid-state is of considerable interest for the development of novel organic electronic materials. In this study, we investigated the effect of combining of two types of supramolecular interaction with different geometric requirements, amide hydrogen bonding and pi-interactions, on the pi-overlap between calamitic pi-conjugated cores. To this end, we prepared two series of bithiophene diesters and diamides with methylene, ethylene, or propylene spacers between the bithiophene core and the functional groups in their terminal substituents. The hydrogen-bonded bithiophene diamides showed significantly denser packing of the bithiophene cores than the diesters and other known alpha,omega-disubstituted bithiophenes. The bithiophene packing density reach a maximum in the bithiophene diamide with an ethylene spacer, which had the smallest longitudinal bithiophene displacement and infinite 1D arrays of electronically conjugated, parallel, and almost linear N-H center dot center dot center dot O=C hydrogen bonds. The synergistic hydrogen bonding and pi-interactions were attributed to the favorable conformation mechanics of the ethylene spacer and resulted in H-type spectroscopic aggregates in solid-state absorption spectroscopy. These results demonstrate that the optoelectronic properties of pi-conjugated materials in the solid-state may be tailored systematically by side-chain engineering, and hence that this approach has significant potential for the design of organic and polymer semiconductors.