In　this　paper,　2-hydroxypyridine　(2-HP)　and　polyethyleneimine　(PEI)　were　selected　as　ligand　and　additive,　respectively,　in　a　cyanide-free　silver　electroplating　bath.　Adsorption　behaviors　of　2-HP　and　PEI　at　silver　electrodes　were　investigated　by　means　of　potential-dependent　surface-enhanced　Raman　spectroscopy　(SERS).　The　adsorption　configuration　variations　of　2-HP　and　PEI　at　the　silver　surface　with　the　negative　shift　of　potential　were　discussed　according　to　the　SERS　analysis.　The　possible　effect　of　2-HP　and　PEI　on　the　silver　electroplating　process　was　also　proposed.　In　the　silver　electroplating　process,　the　SERS　signal　variations　of　2-HP　with　the　negative　shift　of　potential　were　mainly　due　to　the　deposits＇　morphology　change.　In　the　presence　of　PEI,　fine　grains　and　smoother　surfaces　are　observed　from　the　images　of　atomic　force　microscopy　of　the　silver　deposits.