Assembling ultrahigh-molecular-weight (UHMW) block copolymers (BCPs) in rapid time scales is perceived as a grand challenge in polymer science due to slow kinetics. Through surface engineering and identifying a nonvolatile solvent (propylene glycol methyl ether acetate, PGMEA), we showcase the impressive ability of a series of lamellar poly(styrene)-block-poly(2-vinylpyridine) ( PS-b-P2VP) BCPs to selfassemble directly after spin-coating. In particular, we show the formation of large-period (approximate to 111 nm) lamellar structures from a neat UHMW PS-bP2VP BCP. The significant influence of solvent-polymer solubility parameters are explored to enhance the polymer chain mobility. After optimization using solvent vapor annealing, increased feature order of ultralarge-period PS-b-P2VP BCP patterns in 1 h is achieved. Isolated metallic and dielectric features are also demonstrated to exemplify the promise that large BCP periods offer for functional applications. The methods described in this article center on industry-compatible patterning schemes, solvents, and deposition techniques. Thus, our straightforward UHMW BCP strategy potentially paves a viable and practical path forward for large-scale integration in various sectors, e.g., photonic band gaps, polarizers, and membranes that demand ultralarge period sizes.