A series of poly(4-tert-butylstyrene-block-2-vinylpyridine) [P(tBuSt-b-2VP)] block copolymers (BCPs) with varying volume fractions, molecular weights, and narrow dispersities were synthesized from the commercially available monomers by sequential living anionic polymerization. The copolymers were thoroughly characterized by H-1 NMR spectroscopy, size exclusion chromatography, thermal gravimetric analysis, and differential scanning calorimetry (DSC). To examine the effect of the tert-butyl group on the effective interaction parameter (chi(eff)) relative to poly(styrene-block-2-vinylpyridine) [(P(S-b-2VP)], the self-assembly of symmetric copolymers was studied by small-angle X-ray scattering (SAXS) and transmission electron microscopy. Order-to-disorder transitions (ODTs) were identified by both DSC and SAXS on five copolymers, to define the equation chi(eff)(T) = (67.9 +/- 1.3)/T - (0.0502 +/- 0.0029), which shows a higher enthalpic contribution to chi(eff) than P(S-b-2VP) and approximately 1.5 times larger chi(eff). This enables a minimum full pitch of 9.6 nm for the symmetric copolymers. Asymmetric copolymers were also examined for bulk self-assembly by SAXS and TEM, exploring both P2VP and PtBuSt cylindrical phases with diameters as small as 6 nm. Feasibility of thin film assembly by thermal annealing was demonstrated for a P2VP cylinder forming BCPs to yield parallel cylinders that were seeded with Pt ions and etched to yield Pt nanowires with diameters as small as 5.8 nm.