Backbone selective solvent CN gives rise to coiled polymers with a persistence length of 4.5 nm and amorphous aggregates within which polymer chains are disordered and linked only by side-chain association with a lamellar stacking distance dl of 2.4 nm. This leads to a direct crystallization assembly pathway whereby growth of π-stacked crystals can be guided by the solution coating process. The resultant film shows a high degree of alignment (with dichroic ratios RUV-vis of 3.35 and RGIXD of 11.79) and reduced paracrystalline disorder and thus exhibits enhanced charge carrier mobility µFET (0º) = 1.56 ± 0.14 cm 2 V -1 s -1 and charge transport anisotropy (µFET (0º) / µFET (90º) = 5.2) in OFET devices. In mutual solvents like DCB, polymers adopt a helical conformation with a persistence length of 6.4 nm and aggregate into semicrystalline nanofiber aggregates with a diameter around 30 nm. Polymers inside aggregates show both π-π stacking (dπ = 4.37 Å) and lamella stacking (dl = 2.3 nm) due to balanced backbone and side chain interactions. Such nanofiber aggregates are usually believed to promote aligned and ordered thin film morphology. However, in this case, the twisted nanofiber aggregates assemble into chiral LC phases as concentration surpass a threshold during solution coating. The twinned domain in the twist-bent mesophase is carried over into the thin film, resulting in reduced degree of alignment (with RUV-vis of 0.64 and RGIXD of 0.58) and increased paracrystalline disorder. This further leads to inferior charge transport property with a mobility µFET (0º) = 0.50 ± 0.09 cm 2 V -1 s -1 and an anisotropy µFET (0º) / µFET (90º) = 1.56. For PII-2T/decane solution, polymers have the most planarized conformation with a persistence length of 7.4 nm and are tightly packed though strong π-π interactions forming 100-nm wide fibers.