A novel asymmetrically substituted dicyano-tri-tert-butylphthalocyanine ((CN)(2)BuPc) with rectifying, behavior has been synthesized. The morphology and conductive properties of (CN)(2)BuPc Langmuir-Blodgett (LB) films on mica and highly ordered pyrolytic graphite (HOPG) substrates were studied by atomic force microscopy (AFM) and scanning tunneling microscopy (STM), in air at 22degreesC. The average area of each (CN)(2)BuPc molecule obtained from the AFM topography in situ is ca. 73.6 Angstrom(2), which is in good agreement with the result of ca. 74 Angstrom(2) obtained from the pi-A isotherm curve of a LB film. This indicates that the molecules are standing edge-on, tilted by 38degrees against the surface normal of the substrate. The conductive properties for the 7-layer LB films of (CN)(2)BuPc were studied by STM with a tungsten tip. The asymmetric I-V curve revealed a type of rectifying behavior for a negative and a positive bias. A feature model of the intramolecular and intermolecular charge transfer is presented. It not only interprets electron transfer from electron-donor to electron-acceptor molecules via a molecular "bridge", but also the tunneling effect through intermolecular charge transfer.