An electodeposition method has been developed for depositingE.coli. RNA polymerase onto a monoatomically flat gold surface. The scanning tunneling microscope has been used to image this enzyme in a high‐humidity or water/glycerol environment, which allows direct observation without metal coating. The deposition technique is reproducible enough to allow optimization of the deposition parameters for controlled electrodeposition. Time‐dependence studies were conducted to help determine the binding mechanism of the protein. The enzyme molecules appear as ordered arrays, amorphous features, or ‘‘jaw‐shaped’’ molecules depending on the deposition conditions used. The ‘‘jaw‐shaped’’ molecules closely resemble those observed by electron microscopy. In some of these a groove 22 Å wide can be seen.