Nafion-modified coatings can enhance the detection performance of bismuth film electrodes (BFEs). In this work, different coatings (graphene sheets (GS), carbon nanotubes (CNTs), activated carbon (AC), bismuth (Bi), and bismuth trioxide (Bi 2 O 3 )) were prepared by Nafion-assisted electrophoretic deposition (EPD). For successful EPD in ethanol, 0.1 mM NaOH + 0.1 g•L −1 Nafion is suggested as a suitable biadditive. With the in situ formation of a BFE on a coating via the square wave anodic stripping voltammetry (SWASV) method, the GS coating prepared by Nafion-assisted EPD exhibits better detection sensitivity and repeatability than the GS coating prepared by the drop method. Therefore, based on the result that the coatings of GS, CNT, AC, Bi, and Bi 2 O 3 can be prepared by EPD with the biadditives of NaOH + Nafion, as well as the fact that both Nafion and EPD can help improve the detection sensitivity of the BFEs formed on these coatings, a novel and general strategy for designing a series of Nafion-modified single-component coatings or bicomposite coatings to form BFEs with good detection performance can be feasibly realized via electrophoretic codeposition.