Camphorquinone　(CQ)-mediated　one-pot　polyol　methods　are　developed　to　synthesize　silver　right　bipyramids　and　nanocubes.　Morphology　control　between　silver　right　bipyramids　and　nanocubes　is　conducted　by　adjusting　FeCl3　concentration.　Silver　right　bipyramids　with　an　average　size　of　170 nm　and　a　yield　of　87%　are　obtained　with　0.11 mm　FeCl3,　while　silver　nanocubes　with　an　average　size　of　120 nm　and　a　yield　of　70%　are　obtained　with　0.04 mm　FeCl3.　The　as-synthesized　Ag　right　bipyramids　and　nanocubes　fabricate　Surface-enhanced　Raman　scattering　(SERS)　substrates　with　good　signal　reproducibility　to　detect　the　Rhodamine　6G　with　concentrations　down　to　10−12m.　The　SERS　performance　of　silver　right　bipyramids　larger　than　100 nm　is　experimentally　investigated.　A　comparison　of　the　Raman　enhancement　effect　between　Ag　right　bipyramid　and　nanocube　is　conducted　by　comparing　the　enhancement　factors　of　as-fabricated　Ag　right　bipyramid　and　nanocube　SERS　substrates.　The　Ag　right　bipyramid　and　nanocube　SERS　substrates　are　obtained　at　the　same　experimental　condition,　and　their　enhancement　factors　are　calculated　to　be　3.11 × 104　and　2.37 × 104,　respectively.　The　fabricated　sensitive　SERS　substrates　can　potentially　be　used　for　ultrasensitive　detection　of　analytes　in　applications　such　as　food　safety　and　environmental　monitoring.　©　2024　Wiley-VCH　GmbH.