We study relations among the side-chain asymmetry, structure, and order-disorder transition (ODT) in hairy-rod-type poly(9,9-dihexylfluorene) (PF6) with two identical side chains and atactic poly(9-octyl-9-methyl-fluorene) (PF1-8) with two different side chains per repeat. PF6 and PF1-8 organize into alternating side-chain and backbone layers that transform into an isotropic phase at T(PF6) and T(PF1−8). We interpret polymers in terms of monodisperse and bidisperse brushes and predict scenarios TT and T∼T for high and low grafting densities (the side-chain length above or below the average grafting distance). Calorimetry and x-ray scattering indicate the condition T(PF6)∼T(PF1−8) following the low grafting prediction. PF6 side chains coming from the alternating backbone layers appear as two separate layers with thickness H(PF6), whereas PF1-8 side chains appear as an indistinguishable bilayer with a half thickness (PF1−8)/2≈(PF6). The low grafting density region is structurally possible but not certain for PF6 and confirmed for PF1-8.
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