A novel experimental procedure to study the factors that contribute to background silver staining in sodium dodecyl sulphate‐polyacrylamide gel electrophoresis (SDS‐PAGE) is described. A mechanism is proposed for background silver staining, which was found to result primarily from the redox initiator system using ammonium persulphate (APS) and an amine such as N,N,N′,N′‐tetramethylethylenediamine (TEMED).