A series of liquid-crystalline (LC) pi-conjugated oligothiophenes bearing three or two alkoxy chains at their extremities has been designed and synthesized. These polycatenar oligothiophenes form various LC nanostructures including smectic, columnar, and micellar cubic phases, These properties depend on the number and length of the terminal alkoxy chains. The hole mobilities for the oligothiophenes have been measured. The layered smectic structures and columnar structures are capable of transporting holes, leading to mobilities of up to 0.01 cm(2) V-1 s(-1), The columnar LC assemblies have also been explored to produce linearly polarized light-emission. Fine red polarized fluorescence is observed from a uniaxially aligned film of the oligothiophene. The redox properties of the oligothlophenes both In solutions and in films have been examined. The oligothiophenes exhibit electrochromism upon applying an oxidative potential. The present design strategy is useful for fabricating a variety of functional electro-active molecular assemblies.