Three distinct types of poly(3-hexylthiophene)(P3HT)-based crystals were developed using unseeded and seeded protocols. First, unseeded flat fibrillar and scrolled half ring-like crystals were prepared by isothermal crystallization of homo-P3HT and P3HT-b-poly(ethylene glycol) (PEG) block copolymers. Anisottopic accumulation of grafted coily PEG blocks on the opposite surfaces of P3HT half-rings having extended backbones reflected Scrolling, and their subsequent crystallization also further intensified this scrolling. The PEGs assembled into lamellae on both sides of P3HT half-rings with dissimilar crystalline features, i.e., the outer PEG lamella was thicker (17.4 rim) and wider (23.1 nm) compared to the inner one (15.0 and 18.1 nm). Furthermore, the crystallinity of PEG coily blocks accumulated on the P3HT crystals did not change the extended state of P3HT backbones (17.5 nm) and also the thickness of half-rings (11.0 nm). Second, with seeding homogeneous P3HT(7000)-b-PEG(5000) solution using homo-PEG(5000) tiny crystals, the cubic PEG single crystals were sandwiched between grafted regioregular P3HT chains (>99%). The appearance of (020)(P3HT) and (100)(P3HT) spots for tethered P3HTs beside (120)(PEG) prisms demonstrated flat-on orderly tethered P3HT backbones oil:the PEG single crystalline substrate. Via conjunction between block copolymer and homopolmer single crystals in channel (PEG)-/wire (P3HT-covered PEG)/channel (PEG) epitaxials, the P3HT rigid brushes were found to be extended (17.35 nm) on lamellar PEG substrate (6.15 nm). Third, when hoinogenized P3HT(7000)-b-PEG(5000) solutions were seeded by homo-P3HT(7000) tiny crystals, the edge-on orientated fibrillar P3HT single crystals were acquired: Although the thickness (20-22 nm) and length (60-63 mu m) of P3HT(7000)-b-PEG(5000) fibrillar single crystals resembled those of homo-P3HT(7000) ones, their backbone lamination in the c axis were significantly different (2 versus 21); because the P3HT,backbones were not capable of laminating from the coily block sides.