Cyclic voltammetry (CV) has been combined with surface plasmon resonance (SPR) for probing electrochemical deposition and redox‐initiated film reorganization and conformational changes. However, the varying potential during CV scans leads to unwanted SPR background changes and complicates interpretation of SPR signals. In this work, we show that, when SPR is coupled with CV, the background correction for underpotential deposition of copper and electropolymerization of aniline is either inaccurate or difficult to perform. For accurate thickness measurements of electrodeposited films, potential‐step (PS) chronoamperometry is a method of choice to combine with SPR. The theory that interprets double‐layer charging is used to explain the advantage of PS chronoamperometry over CV in quantifying the thickness of electrodeposited thin films. The influence of the double‐layer charging on the potential‐induced SPR signal change was analyzed, and the results were used to optimize experimental parameters for PS‐SPR. Overall, PS‐SPR is easier to operate, simpler in data interpretation, and more accurate for the film thickness measurement.