We have developed plasma chemical vaporization machining by using a microelectrode for the fabrication of small complex-shaped optical surfaces. In this method, a 0.5 mm diameter pipe microelectrode, from which processing gas is drawn in, generates a small localized plasma that is scanned over a workpiece under numerical computer control to shape a desired surface. A 12 mm x 12 mm nonaxisymmetric mirror with a maximum depth of approximately 3 microm was successfully fabricated with a peak-to-valley shape accuracy of 0.04 microm in an area excluding the edges of the mirror. The average surface roughness was 0.58 nm, which is smooth enough for optical use.