Insulated conductive molecules, in which the π-conjugated compounds are covered by a cyclic protective sheath, have attracted considerable attention because of their potential applicability in next-generation molecular electronic devices. We have developed new methods of synthesizing insulated π-conjugated molecules involving the self-inclusion of rotaxane precursors linking π-conjugated units as a guest and permethylated cyclodextrin (PM CD) as a macrocyclic host. A new method for synthesizing insulated molecular wire (IMW) through the polymerization of insulated π-conjugated molecules as monomers was also developed. The obtained IMWs are highly soluble in organic solvents and have a high covering ratio, rigidity, and photoluminescence efficiency; further, they show high charge mobility, even in the solid state. This paper also highlights a new type of molecular wiring method based on the polymerization or co-polymerization of an insulated π-conjugated monomer between nanosized electrodes.