A low-molecular-weight poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (designated as Lw-pBTTT-C16) in a fair solvent (chlorobenzene, CB) displays peculiar structural, mechanical, and electronic features during sol-gel transition. Using comprehensive (multiscale) dynamic/static analysis schemes, the Lw-pBTTT-C16/CB solution (10 mg mL-1) is shown to capitalize on rod associations and networking to form a gel, in stark contrast with its high-molecular-weight companion previously reported to form gels through hierarchical colloidal bridging. The present study reveals, however, that the molecular weight of pBTTT-C16 has a subtle impact on the gelation behaviors through the rarely recognized, contrasting supramolecular conformations (rod-like vs. wormlike) of the aggregate clusters fostered in the pristine solution. The ac conductivity nearly doubles as a result of improved (mesoscale) packing of cylindrical aggregates near the gel state as well as enhanced backbone rigidity of the constituting chains. Other distinguishing features include: (1) there is no real crossover of the dynamic moduli (G' and G'') upon increasing the temperature from gel (T = 15 °C) to solution (T = 80 °C) states. (2) The gel is about a hundredfold softer in dynamic modulus, yet more resilient with a fivefold increase in the yield strain. Both viscoelastic features are expected to greatly benefit the gel processability. (3) The coexistent microgels and cylinder (aggregate) bundles form a peculiar gel network that has not been reported previously with polymer or colloidal gels. The overall findings provide new mechanistic insight into the phenomenological effects of molecular weight for the pBTTT-Cn series in solution, sol, gel, and thin film.