The present paper reviews the widely used surface microstructural investigation technique and micro/nano nondestructive evaluation(NDE) technique which is able to evaluate the surface and subsurface. In general, the micro/nano defects and microstructural state of surface have great influence on the mechanical, physical, and chemical properties of bulk materials. The investigation technique of surface microstructure is possible to evaluate the defects and microstructural state with high reliability. The various applications and developments of each inspection technique have been introduced. Consequently, it is thought that the technique developments and applications of micro/nano NDE in nondestructive industries are extensively possible hereafter.