Molecular-resolution images of an electrochemically prepared single crystal of potassium tetracyanoplatinate bromide complex (KCP(Br)) were recorded by atomic force microscopy during a tip-induced surface-modification process in which the probing tip scraped off the topmost surface layer by layer. Two kinds of molecular images on the (010) face of the KCP(Br) crystal correspond to alternate layered structures consisting of tetracyanoplatinate layers and interstitial ions. One molecular arrangement was assigned to cyanide Ligands and interstitial K+ and Br- ions, in good agreement with that obtained from X-ray diffraction. The other corresponds to rearranged interstitial ion (K+ and Br-) layer. The rearrangement of the interstitial ions during the tip-induced surface modification involves both loss of half of the K+ ions so as to preserve electroneutrality of the surface and to stabilize the dislocations of the remaining ions. The present AFM imaging process during the tip-induced surface modification provides mechanistic information on molecular and ionic arrangements on the topmost surface.