The large majority of semiconducting polymers based on poly(alkylthiophene)s with either linear or branched alkyl side chains are reported to π-stack in their crystalline phases. In regioregular poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT), however, π−π interactions are absent due to the presence of the bulky 2,5-dioctylphenyl side groups. In this work, high levels of crystallinity and orientation are created in thin films of PDOPT aligned on substrates of naphthalene by slow directional epitaxial crystallization of the side chains. Depending on molecular weight, both edge-on and flat-on lamellar crystals are obtained. As for poly(3-hexylthiophene) (P3HT), electron microscopy imaging reveals a transition from extended to folded chain crystallization in PDOPT for M n ≈ 12.7 kDa. The high orientation and crystallinity result in high anisotropy in UV−vis absorption and photoluminescence with well-defined vibronic structures. The single-crystal-like electron diffraction patterns are further used to refine a structural model of PDOPT (a = 29.09 Å, b = 10.45 Å, c = 7.72 Å, α = β = γ = 90°, and space group P21/c). Uniquely, crystalline PDOPT features perfectly planarized chains despite the absence of π-stacking between polythiophene backbones. The octyl side chains are interdigitated and crystallize in a dense subcell which is compared to that of other semiconducting polythiophenes, e.g. form I poly(3-hexylthiophene) and poly(2,5-bis(3-dodecyl-2-yl)thieno[3,2b]thiophene), to draw a trend between overall crystallinity and density of the side chain packing.