Novel calamitic liquid crystals having an electron-deficient isoquino[8,7-h]isoquinoline moiety as a core, 2,8-didecylisoquino[8,7-h]isoquinoline (10-IQIQ-10) and 2,8-didodecylisoquino[8,7-h]isoquinoline (12-IQIQ-12), were prepared, and their phase transition behaviors, HOMO and LUMO levels, and charge carrier transport properties were investigated. 12-IQIQ-12 showed a highly ordered smectic H phase at around 140 to 150 degrees C and a low-lying LUMO level of -3.33 eV. Time-of-flight measurements revealed field-independent ambipolar transport characterized by mobility on the order of 10(-4) cm(2) V-1 s(-1) at the highly ordered smectic phase.