Mussel-inspired polydopamine has been widely used in capillary electrophoresis as a facile and universal tool for the surface modification of capillary, mainly due to its versatility, stability, strong adhesiveness, and biocompatibility properties. In this review, the recent development of mussel-inspired surface chemistry with rapid deposition of polydopamine was introduced, and the recent applications of polydopamine in capillary electrophoresis (2011-July 2018) were summarized into four main aspects, namely, sample pretreatments, functional coatings, codeposition coatings, and intermediate coatings. Further study may be focused on clarifying the mechanisms of polydopamine formation and polydopamine-assisted codeposition, and expanding coatings methods to plant polyphenols.