A simple method for fabricating silicon electrodes with various shapes and gap widths was designed using the special properties of anisotropic tetramethylammonium hydroxide (TMAH) wet etching and local anodic oxidation (LAO). A statistical system was used for the optimization of the parameters of the LAO process to facilitate a better understanding and precise analysis of the process. Analyses of the interaction effects among the significant factors of LAO showed that the relative humidity and applied voltage were interdependent. They had the strongest interaction effect on the dimensions of the oxide mask. TMAH with a concentration of 25 was used as an etchant solution in (100) silicon with a rectangular oxide mask. The observed undercutting at convex corners, tip shape of emitters and gap widths of electrodes were exactly consistent with theoretical studies. Combination of the LAO method and anisotropic TMAH wet etching was successfully used to fabricate Si nano-gap electrodes. This fabrication method of sharp and round tip emitters was simple, controllable and faster than common techniques. These results indicate that the method can be a new approach for studying the electrical properties of nano-gap electrodes. © 2012 IOP Publishing Ltd.