Hierarchical　micro/nanostructured　TiO2/Ag　substrates　for　surface-enhanced　Raman　scattering　(SERS)　application　are　fabricated　by　depositing　Ag　nanoparticles　on　the　surface　of　TiO2　hierarchical　micro/nanostructures,　which　are　formed　by　combining　femtosecond　laser　structuring　with　scalable　hydrothermal　treatment.　Our　results　show　that　the　morphology　of　hierarchical　micro/nano　TiO2/Ag　architectures　can　significantly　influence　SERS　performance.　Compare　with　one-dimensional　TiO2/Ag　nanostructures　hydrothermally　fabricated　on　laser　untreated　Ti　surface,　a　four-fold　enhancement　is　shown　in　the　SERS　signal　with　excellent　reproducibility.　Most　importantly,　enhancement　is　significantly　stronger　in　the　valleys　of　our　microstructures　than　on　the　hills　due　to　geometrical　orientation　of　nanostructures　on　the　surface　of　the　microstructure.　The　site　predictability　for　SERS　enhancement　is　one　of　the　major　roadblock　for　SERS　applications.　Present　study　provides　an　effective　way　to　enhance　the　site　predictability　for　optimal　SERS　in　addition　to　a　significant　enhancement　in　signal　strength.