We have developed a microscope for the acquisition of optical sum frequency (SF) intensity images and have observed two types of samples. We have observed resonant electronic and vibrational images of the H‐Si(111) surface in UHV conditions after IR light irradiation of pulse width ∼6 µs. In the resonant SF intensity images, we identified the images of areas covered by SiH species. Nonresonant SF signals appeared in the area irradiated by the IR light pulses, originating from a nonlinear optical transition involving the surface electronic levels in the Si dangling bonds. We also found an unidentified bonding state on the edges of the irradiated area in some light conditions. We have also observed images of a water plant Chara fibrosa by this SF microscope in air. We found that the starch is observed selectively in the oogonium of the water plant and the amylopectin was found to be one of the main ingredients in it. Copyright © 2010 John Wiley & Sons, Ltd.