The　fabrication　of　porous　silicon　with　double　band　photoluminescence　(PL)　by　chemical-assisted　1064　nm　picosecond　(ps)　laser　irradiation　of　polysilicon　is　presented.　The　hybrid　method　includes　controlling　of　the　laser　scanning　interval,　number　of　scans　to　form　dense　micropores,　and　subsequently,　short-　time　acid　corrosion　to　form　fine　nanostructure.　Along　with　the　stable　red　PL　visible　to　the　naked　eye,　a　new　violet　PL　band　at　432　nm　existed　in　the　fabricated　samples.　The　double　band　photoluminescence　was　mainly　attributed　to　the　prepared　micro/　nano　hierarchical　structure.　Moreover,　dangling　bond　defects　formed　by　high-　energy　photon　impinging　acted　as　the　catalyzer　in　the　subsequent　acid　corrosion　resulted　in　good　passivation　of　the　nanostructure　with　the　formation　of　Si-H　and　Si-O　bond,　which　also　contributed　to　the　stable　photoluminescence.　The　maximum　surface　porosity　of　the　samples　was　concluded　to　be　90.48%　which　also　bring　good　hydrophobicity　for　the　prepared　samples.　(C)　2016　Laser　Institute　of　America.