We fabricated a micrometer-long supramolecular chain in which pi-conjugated polyrotaxane was coupled. A new experimental setup was designed and constructed, and the simultaneous direct imaging of the structure and fluorescent function was achieved. Furthermore, we identified the formation of a polymer intertwined network and observed novel fluorescence due to a long-range interaction via this intertwined network over a distance of 5 mu m or more without quenching over 15 min in the near field. (c) 2005 Wiley Periodicals, Inc.