The intrinsic, local-scale hole and electron mobilities at the interface between perylenediimide (PDI)-based liquid crystalline organic semiconductors and insulating polymers were evaluated by field-induced time-resolved microwave conductivity (FI-TRMC). The PDI liquid crystals having alkyl and semifluoroalkyl tails showed ambipolar hole and electron mobilities of 0.2 and 0.3 cm(2) V-1 s(-1), respectively. In contrast, the PDI having triethylene glycol and semifluoroalkyl tails showed no significant conductivity, suggesting an important role of side chain structures on the charge transport properties. The FI-TRMC technique demonstrated here serves as a powerful tool to screen out the interfacial structure of liquid crystalline semiconductor materials.