A programmable interconnect structure and method of operating the same provides a programmable interconnection between electrical contacts. The interconnect includes material that has a reversibly programmable resistance. The material includes a molecular matrix with ionic complexes distributed through the molecular matrix. Application of an electrical field or electric current causes the molecular composite material to assume a desired resistivity (or conductivity) state. This state is retained by the molecular composite material to thus form a conductive or a non-conductive path between the electrical contacts.