Based on the widely used wet metal-assisted electroless etching, we develop in this work a novel vapor-phase silver-assisted chemical etching (VP-Ag-ACE) suitable for the elaboration of highly doped p-silicon (Si) nanostructures with strong, visible, and multi-peak photoluminescence (PL) emissions. The lateral and vertical etching rates (LER and VER) were discussed based on the etching mechanism of the VP-Ag-ACE. The antireflective suitability of the vapor-etched layer has been evaluated by a reflectivity measurement and exhibits reflectivity values lower than 3%. The PL emission at both room and low temperatures emissions were deeply discussed and correlated with the structural properties of the Si morphologies and their surface states based on the FTIR results.