The macro and micro morphology of the Si surface, depending on noble metal ion concentration in etching solution, prepared by metal assisted etching were investigated. We defined the morphology of etched Si in four types, and developed the phase diagram of Si morphology. Mixture of silver nitrate (AgNO3) and hydrofluoric acid (HF) was used as an electroless-plating bath of Ag, as well as etching solution of Si. The morphology of the etched Si surface as function of concentration of AgNO3 in etching solution was observed by SEM. With increasing concentration of the AgNO3 in the etching solution, the surface of etched Si tended to be porous structure with very fine pores of a few nm (porous Si). When concentration of AgNO3is low, single crystal Si nanowires with a smooth surface without pores were observed.