This article concerns the detailed investigations on the silver dendrite-assisted growth of single-crystalline silicon nanowires, and their possible self-assembling nanoelectrochemistry growth mechanism. The growth of silicon nanowires was carried out through an electroless metal deposition process in a conventional autoclave containing aqueous HF and AgNO3 solution near room temperature. In order to explore the mechanism and prove the centrality of silver dendrites in the growth of silicon nanowires, other etching solution systems with different metal species were also investigated in this work. The morphology of etched silicon substrates strongly depends upon the composition of the etching solution, especially the metal species. Our experimental results prove that the simultaneous formation of silver dendrites is a guarantee of the preservation of free-standing nanoscale electrolytic cells on the silicon substrate, and also assists in the final formation of silicon nanowire arrays on the substrate surface.