Mesomorphic and electron transport properties are compared for liquid-crystalline (LC) perylene tetracarboxylic bisimide (PTCBI) derivatives bearing linear disiloxane and trisiloxane chains, as well as bis(trimethylsiloxanyl)methylsilyl(trisiloxan-2-yl) groups. In contrast to alkyl-substituted analogues, the PTCBI derivative bearing bulky trisiloxan-2-yl moieties exhibits a more ordered columnar phase and higher electron mobility compared to that bearing linear trisiloxane chains. In spite of the bulkiness, the trisiloxan-2-yl moieties do not inhibit closed π–π stacking within the columnar aggregates. Therefore the electron mobility in the ordered columnar phase of the compound bearing the branched trisiloxan-2-yl moieties was 0.05 cm² V⁻¹ s⁻¹ at room temperature and it exceeded 0.1 cm² V⁻¹ s⁻¹ at 120 °C.